Use in perfumery of carboalkoxy alkyl norbornanes

ABSTRACT

Use in perfumery are compounds both separately and in admixture having the generic structure: ##STR1## wherein the dashed line is either a carbon-carbon single bond or a carbon-carbon double bond and each of R 1 , R 2 , R 3 , R 4 , R 6  and R 7  represents hydrogen or methyl with the proviso that one of R 1 , R 2 , R 6  and R 7  is methyl and each of the other of R 1 , Rhd 2, R 6  and R 7  is hydrogen and R 3  and R 4  are not both methyl; wherein R 5  represents C 1  -C 4  alkyl are disclosed.

This application is a divisional of application for U.S. Ser. No.206,466 filed on Nov. 13, 1980, now U.S. Pat. No. 4,312,888 issued onJan. 26, 1982, which, in turn, is a continuation-in-part of applicationfor U.S. Ser. No. 133,870 filed Mar. 25, 1980, now U.S. Pat. No.4,319,036 issued on Mar. 9, 1982.

BACKGROUND OF THE INVENTION

The present invention relates to carboalkoxy alkyl norbornanes havingthe generic formula: ##STR2## wherein the dashed line represents eithera carbon-carbon single bond or a carbon-carbon double bond; R₁, R₂, R₃,R₄, R₆ and R₇ represents hydrogen or methyl; with the proviso that oneof R₁, R₂, R₆ and R₇ is methyl and each of the other of R₁, R₂, R₆ andR₇ is hydrogen; and with the further proviso that R₃ and R₄ are not bothmethyl, produced by the novel process of our invention, and to novelcompositions using one or more of such norbornane derivatives to alter,modify or enhance the flavor and/or aroma of consumable materials orimpart flavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural material, some of which may be inshort supply, and to provide more uniform properties in the finishedproduct.

Fruity, burnt fruit-like, raspberry, sweet, seedy, berry-like, redberry-like, blueberry-like, spicy, black pepper-like, herbaceous,clove-like, vermouth-like, strawberry-like, wild strawberry-like,camphoraceous and balsamic aromas with fruity burnt fruit-like,raspberry, seedy, sweet berry-like, red berry-like, blueberry-like,spicy, black pepper-like, herbaceous, clove-like, vermouth-like,strawberry-like, wild strawberry-like, camphoraceous, balsamic andbitter tastes are particularly desirable for many uses in foodstuffflavors, chewing gum flavors, toothpaste flavors and medicinal productflavors.

Spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity,berry-like, juicyfruit, woody, piney, blueberry, banana, green,herbaceous, strawberry-like and dill aroma and taste characteristicsboth prior to and on smoking in the mainstream and in the side stream.

Intense and pleasant fruity, strawberry-like, raspberry, Resedabody-like, banana-like, creamy, camphoraceous, herbaceous, sweet, spicy,woody, eucalyptol-like, rum/butterscotch-like, balsamic, green, minty,borneol-like and "medicinal" aromas with strong camphor, minty andcalamnus-like undertones are desirable in several types of perfumecompositions, perfumed articles and colognes.

Arctander, "Perfume and Flavor Chemicals", 1969, Volume I discloses theuse in perfume compositions and in foodstuff flavors of camphenecarbinyl acetate thus:

"1029: 2,2-Dimethyl-Delta-2-betanorbornane-2-ethylacetate

"Camphene carbinyl acetate". ##STR3## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably not welldefined single chemicals, and great variations in odor have beenobserved.

This ester has been developed in line with the research on Sandalwoodtype odors. The parent alcohol "Camphene carbinol" was once considereduseful as a Sandalwood type material, but is has found more use as asweetening and enriching ingredient in sophisticated Pine fragrances.The title ester finds limited use in perfume compositions of woodycharacter, Fougeres, Pine fragrances, etc. and it blends very well withthe Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks,etc."

Mellor and Webb, J. Chem. Soc. Perkin Trans II, 1974 (I) 26-31 disclosesproduction of the compounds having the structures: ##STR4## togetherwith several other methyl substituted isomers thereof in admixture,according to the reaction: ##STR5## The Mellor and Webb article however,does not disclose the reaction to take place at low temperatures in thepresence of an alkyl aluminum halide or dialkyl aluminum halide wherebybut two isomers are produced in a controlled fashion in high yields thusyielding an organoleptically acceptable mixture of carboalkoxynorbornane derivatives.

Thus, nothing in the prior art indicates production for organolepticuses of compounds having the generic structure: ##STR6## wherein thedashed line represents a carbon-carbon single bond or a carbon-carbondouble bond and R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined above.

U.S. Pat. No. 4,143,074 discloses, generically, compounds which areesters and contain the norbornyl moiety having the structures: ##STR7##wherein either or both of R₁ or R₂ is hydrogen or lower alkyl, R₃ ishydrogen or lower alkyl and n is zero or 1 and in addition, the compoundhaving the structure: ##STR8## wherein R₆ is alkyl having from one up toeight carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 sets forth the GLC profile for the reaction product of Example Icontaining compounds having the structures: ##STR9##

FIG. 2A is the NMR spectrum for fraction 8 of the distillation productof the reaction product of Example I having the structure: ##STR10##

FIG. 2B represents the NMR spectrum for fraction 2 of the distillationproduct of the reaction product of Example I having the structure:##STR11##

FIG. 3A represents the infrared spectrum for fraction 8 of thedistillation product of the reaction product of Example I having thestructure: ##STR12##

FIG. 3B represents the infrared spectrum for fraction 2 of thedistillation product of the reaction product of Example I having thestructure: ##STR13##

FIG. 4 represents the mass spectrum for the reaction product of ExampleI containing compounds having the structures: ##STR14##

FIG. 5 represents the GLC profile for the reaction product of Example IIcontaining compounds having the structures: ##STR15##

FIG. 6A represents the NMR spectrum of peak 1 of the GLC profile of FIG.5 consisting essentially of the compound having the structure: ##STR16##

FIG. 6B represents the NMR spectrum for fraction 6 of the distillationproduct of the reaction product of Example II consisting essentially ofthe compound having the structure: ##STR17##

FIG. 7A represents the infrared spectrum for peak 1 of the GLC profileof FIG. 5 of the reaction product of Example II consisting essentiallyof the compound having the structure: ##STR18##

FIG. 7B represents the infrared spectrum for fraction 6 of thedistillation product of the reaction product of Example II having thestructure: ##STR19##

FIG. 8 represents the mass spectrum of the reaction product of ExampleII containing compounds having the structures: ##STR20##

FIG. 9 represents the GLC profile of the reaction product of Example IIIcontaining compounds having the structures: ##STR21##

FIG. 10A represents the NMR spectrum for fraction 10 of the distillationproduct of the reaction product of Example III containing the compoundhaving the structure: ##STR22##

FIG. 10B represents the NMR spectrum for fraction 6 of the distillationproduct of the reaction product of Example III containing the compoundhaving the structure: ##STR23##

FIG. 11A represents the infrared spectrum for fraction 10 of thedistillation product of the reaction product of Example III containingthe compound having the structure: ##STR24##

FIG. 11B represents the infrared spectrum for fraction 6 of thedistillation product of the reaction product of Example III containingthe compound having the structure: ##STR25##

FIG. 12 represents the mass spectrum for the reaction product of ExampleIII containing compounds having the structures: ##STR26##

FIG. 13 represents the GLC profile of the crude reaction product (washedbefore distilling) of Example IV containing the compounds having thestructures: ##STR27##

FIG. 14 represents the GLC profile for bulked fractions 7-12 inclusiveof the distillation product of the reaction product of Example IV(conditions: Carbowax column programmed at 80°-122° C. at 8° C. perminute).

FIG. 15A represents the NMR spectrum for the reaction product of ExampleIV containing the compound having the structure: ##STR28##

FIG. 15B represents the NMR spectrum for the reaction product of ExampleIV containing the compound having the structure: ##STR29##

FIG. 16A represents the infrared spectrum for the reaction product ofExample IV containing the compound having the structure: ##STR30##

FIG. 16B represents the infrared spectrum for the reaction product ofExample IV containing the compound having the structure: ##STR31##

FIG. 17 represents the mass spectrum for the reaction product of ExampleIV containing the compounds having the structures: ##STR32##

FIG. 18 represents the GLC profile for the reaction product of Example Vcontaining the compounds having the structures: ##STR33##

FIG. 19A represents the NMR spectrum for fraction 9 of the distillationproduct of the reaction product of Example V containing the compoundhaving the structure: ##STR34##

FIG. 19B represents the NMR spectrum for fraction 1 of the distillationproduct of the reaction product of Example V containing the compoundhaving the structure: ##STR35##

FIG. 20A represents the infrared spectrum for fraction 9 of thedistillation product of the reaction product of Example V containing thecompounds having the structure: ##STR36##

FIG. 20B represents the infrared spectrum for fraction 1 of thedistillation product of the reaction product of Example V containing thecompound having the structure: ##STR37##

FIG. 21 represents the mass spectrum for the reaction product of ExampleV containing the compounds having the structures: ##STR38##

FIG. 22 represents the GLC profile for the reaction product of ExampleVI containing the compounds having the structures: ##STR39##

FIG. 23A represents the NMR spectrum for fraction 14 of the distillationproduct of the reaction product of Example VI containing the compoundhaving the structure: ##STR40##

FIG. 23B represents the NMR spectrum for fraction 4 of the distillationproduct of the reaction product of Example VI containing the compoundhaving the structure: ##STR41##

FIG. 24A represents the infrared spectrum for fraction 14 of thedistillation product of the reaction product of Example VI containingthe compound having the structure: ##STR42##

FIG. 24B represents the infrared spectrum for fraction 4 of thedistillation product of the reaction product of Example VI containingthe compound having the structure: ##STR43##

FIG. 25 represents the mass spectrum for the reaction product of ExampleVI containing the compounds having the structures: ##STR44##

FIG. 26 represents the GLC profile for the reaction product of ExampleVII containing the compounds having the structures: ##STR45##

FIG. 27 represents the NMR spectrum for the reaction product of ExampleVII containing a mixture of the compounds having the structures:##STR46##

FIG. 28 represents the infrared spectrum for the reaction product ofExample VII containing a mixture of the compounds having the structures:##STR47##

FIG. 29 represents the mass spectrum for the reaction product of ExampleVII containing a mixture of the compounds having the structures:##STR48##

FIG. 30 sets forth the GLC profile for the reaction product of ExampleVII-A (bulked fraction 3-5 after distillation) consisting of thecompounds having the structures: ##STR49##

FIG. 31-A sets forth the NMR spectrum for fraction 1 of the distillationproduct of the reaction product of Example VII-A consisting of thecompound having the structure: ##STR50##

FIG. 31-B sets forth the NMR spectrum for peak 2 of the GLC profile ofthe reaction product of Example VII-A consisting of the compound havingthe structure: ##STR51##

FIG. 32-A sets forth the infrared spectrum for fraction 1 of thedistillation product of the reaction product of Example VII-A consistingof the compound having the structure: ##STR52##

FIG. 32-B sets forth the infrared spectrum for peak 2 of the GLC profileof the reaction product of Example VII-A consisting of the compoundhaving the structure: ##STR53##

FIG. 33-A sets forth the mass spectrum for fraction 1 of thedistillation product of the reaction product of Example VII-A consistingof the compound having the structure: ##STR54##

FIG. 33-B sets forth the mass spectrum for peak 2 of the GLC profile ofthe reaction product of Example VII-A consisting of the compound havingthe structure: ##STR55##

FIG. 34 is the GLC profile (conditions: carbowax programmed at 80°-220°C. at 8° C. per minute) of the reaction product of Example XXXIIcontaining the compounds having the structures: ##STR56##

FIG. 35-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 34containing the compound having the structure: ##STR57##

FIG. 35-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 34containing the compound having the structure: ##STR58##

FIG. 36-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR59##

FIG. 36-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR60##

FIG. 37 is the GLC profile for the reaction product of Example XXXIII(conditions: SE-30 column programmed at 80°-220° C. at 8° C. per minute)containing the compounds having the structures: ##STR61##

FIG. 38-A is the NMR spectrum for Fraction 1, Peak 1 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR62##

FIG. 38-B is the NMR spectrum for Fraction 8, Peak 2 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR63##

FIG. 39-A is the infra-red spectrum for Fraction 1, Peak 1 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR64##

FIG. 39-B is the infra-red spectrum for Fraction 8, Peak 2 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR65##

FIG. 40-A is the NMR spectrum for Fraction 2, Peak 1 of the distillationproduct of the reaction product of Example XXXIV containing thecompounds having the structures: ##STR66##

FIG. 40-B is the NMR spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR67##

FIG. 41-A is the infra-red spectrum for Fraction 2, Peak 1 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR68##

FIG. 41-B is the infra-red spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR69##

FIG. 42 is the GLC profile for the reaction product of Example XXXVcontaining the compounds having the structures: ##STR70##

FIG. 43-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 42of the reaction product of Example XXXV containing the compound havingthe structure: ##STR71##

FIG. 43-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 42for the reaction product of Example XXXV containing the compound havingthe structure: ##STR72##

FIG. 44-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR73##

FIG. 44-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR74##

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having the fruity, burnt fruit, raspberry, seedy,sweet, berry-like, red berry-like, blueberry-like, spicy, blackpepper-like, herbaceous, clove-like, vermouth-like, strawberry-like,wild strawberry-like camphoraceous and balsamic aroma characteristicsand flavor characteristics as well as bitter taste characteristics; aswell as novel smoking tobacco and smoking tobacco flavoring compositionshaving spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity,berry-like, juicyfruit, woody, piney, blueberry, banana, green,herbaceous, strawberry-like and dill aroma and taste prior to and onsmoking in both the mainstream and the sidestream; as well as novelperfume compositions, colognes and perfumed articles (e.g., solid orliquid anionic, cationic, nonionic or zwitterionic detergents, fabricsofteners and dryer-added fabric softener articles) having intense andlong lasting fruity, banana, creamy, camphoraceous, strawberry-like,raspberry, reseda body-like, herbaceous, sweet, spicy, woody,eucalyptol-like, rum/butterscotch-like, balsamic, green, minty,borneol-like, and medicinal aromas with strong camphor, minty andcalamnus-like undertones may be provided by utilization of one or moreof the substituted norbornane derivatives having the generic structure:##STR75## wherein the dashed line represents either a carbon-carbonsingle bond or a carbon-carbon double bond and R₁, R₂, R₃, R₄, R₆ and R₇represent either hydrogen or methyl with the proviso that one of R₁, R₂,R₆ and R₇ is methyl and each of the other of R₁, R₂, R₆ and R₇ ishydrogen; and with the further proviso that R₃ and R₄ are not bothmethyl, in foodstuffs, chewing gums, toothpastes, medicinal products,perfume compositions, perfumed articles, colognes and smoking tobaccosas well as smoking tobacco substitutes.

Unless otherwise specified, representations herein are intended toindicate "cis" isomers, "trans" isomers, mixtures of "cis" and "trans"isomers and "endo" isomers and "exo" isomers with respect to thenorbornane ring moiety and dextro and levorotatory isomers as well asracemic mixtures of optical isomers of the norbornane derivatives of ourinvention.

Thus, the generic structure: ##STR76## is intended to mean both "endo"and "exo" isomers having the structures: ##STR77##

The novel substituted norbornane derivatives of our invention useful asindicated supra may be produced by reacting a 1-methylcyclopentadiene or2-methylcyclopentadiene having one of the structures: ##STR78## or amixture of these methylcyclopentadienes defined according to the genericstructure: ##STR79## with an alkyl acrylate derivative defined accordingto the generic structure: ##STR80## in the presence of a specific Lewisacid catalyst at relatively low temperatures (e.g., 0°-50° C.) or in theabsence of a catalyst at relatively high temperatures (e.g., 170°-250°C.).

When using the catalytic process of our invention, an isomer mix will beproduced which contains isomers in proportions and (in some cases)having structures different from the proportions and (in some cases)structures produced using the high temperature reaction of our invention(which reaction is carried out in the absence of catalyst).

The reactant having the structure: ##STR81## represents a "cis" isomeror a "trans" isomer or a mixture of "cis" and "trans" isomers. Thus, the"trans" isomer may be represented by the structure: ##STR82## and the"cis" isomer may be represented by the structure: ##STR83##

When performing the process for preparing compounds useful in thepractice of our invention where the use of a catalyst is required, thecatalyst for the reaction may be an alkyl aluminum dihalide or a dialkylaluminum halide for example RAlCl₂ or R₂ AlCl wherein R representsmethyl, ethyl or n-propyl or i-propyl. The preferred catalyst is ethylaluminum dichloride. Other Lewis acids such as aluminum trichloride,stannic chloride, zinc chloride, ferric chloride and titaniumtetrachloride have been attempted to be used but such attempts haveproved to be unsuccessful with minimal or no yields of product beingproduced. The temperature range of the reaction may vary from about 0°C. up to about 50° C. with ambient temperatures, from 20 up to 30° C.being preferred. The reaction pressure will not affect the yield butconveniently and economically, a reaction pressure of atmospheric ispreferred. Thus, the catalyst for the reaction may be defined accordingto the formula: R_(m) ' AlCl_(n) wherein R' is C₁ -C₃ alkyl and the sum,m+n, equals 3; with m being one or two and n being one to two.

The reaction mass resulting from the catalytic process is a mixture ofcompounds containing unsaturation in the norbornane moieties definedaccording to the generic structures: ##STR84##

When performing the reaction for preparing compounds useful in thepractice of our invention in the absence of catalysts (that is where nocatalyst is required), the reaction temperature is in the range of fromabout 170° C. up to about 250° C. with a temperature of 200° C. beingpreferred. When the reaction is carried out at such high temperatures,the reaction is carried out under pressures greater than atmospheric ina closed pressurized system. The pressure of reaction may vary fromabout 10 psig up to about 100 psig depending on the vapor pressure ofthe reaction mass and depending upon the temperature at which it isdesired to carry out the reaction. Thus, reaction pressures of between10 psig and 100 psig will not in and of themselves affect the yield ofproduct although too high a temperature of reaction will affect theyield of product in view of the higher degree of decomposition and toolow a reaction temperature will affect the yield of product in that thereaction will take an inordinately long period of time in order toachieve a given yield. Thus, it appears that the optimum reactiontemperature in the absence of catalyst is 200° C. Reaction temperaturesbelow 170° C. will not be high enough to effect the initiatingdecomposition of the dimethyl dicyclopentadiene starting material whichit is most practical to use as a precursor of the dimethyldicyclopentadiene.

The reaction mass resulting from the "thermal-non-catalytic" process isalso a mixture of compounds containing unsaturation in the norbornanemoiety defined according the the generic structures: ##STR85## whereinR₃, R₄ and R₅ are as defined above.

The above unsaturated compounds may be used "as is" for their individualorganoleptic properties or mixtures of compounds may be used "as is" fortheir organoleptic properties or the compounds individually or inadmixture may be further hydrogenated using hydrogen gas at superatmospheric pressures. When it is desired to use the compounds "as is"for their organoleptic properties, it is preferable to refine thereaction mass as by fractional distillation or high pressure liquidchromatography thereby creating one or more products usable as set forthabove.

When it is desired to carry out a hydrogenation, the hydrogenation iscarried out preferably on mixtures of products containing compoundshaving unsaturation prepared by the above named Diels-alder reactions.Thus, when carrying out the hydrogenation on a mixture of productscontaining compounds resulting from the catalytic process and having thestructures: ##STR86## wherein R₃, R₄ and R₅ are defined as above,compounds having the structures: ##STR87## will be produced.

When carrying out the hydrogenation on a mixture of products containingthe compounds resulting from the non-catalytic, thermal process andhaving the structures: ##STR88## the compounds having the structures:##STR89## will be produced.

In either case, it is preferable to carry out the hydrogenation atpressures of from about 20 psig up to about 2,000 psig with a pressurerange of from about 40 up to about 80 psig being preferred. It is alsopreferable for the reaction to be carried out in the presence of acatalyst such as Raney Nickel, palladium on carbon, palladium on calciumcarbonate, palladium on barium surfate and platinum. When using thepalladium-salt catalyst, it is preferred to use from about 3% up toabout 12% palladium on salt, for example 5% palladium on calciumcarbonate.

Thus, the reaction sequence which is embodied within our invention whenusing the catalytic procedure may be illustrated as follows: ##STR90##wherein one of R₃ or R₄ is hydrogen and the other of R₃ or R₄ is methyl;wherein R₅ represents C₁ -C₄ lower alkyl; wherein R' represents C₁ -C₃alkyl; and wherein M+N equals three with M being equal to one or two andN being equal to one or two.

Furthermore, the reaction sequence which is embodied within ourinvention when using the high temperature non-catalytic Diels-alderreaction may be illustrated as follows: ##STR91## wherein R₁, R₂, R₃,R₄, R₅, R₆ and R₇ are as defined above.

The following tables set forth the products covered by our invention andthe alkyl acrylate precursor reactant starting materials to be reactedwith the methylcyclopentadienes to produce said products and in additionsets forth the organoleptic properties of the products of our invention:

                  TABLE I                                                         ______________________________________                                        Alkylacrylate                                                                            Reaction Product                                                                            Reaction Product                                     Reactant   Names         Structures                                           ______________________________________                                        Methylcrotonate (catalytic Diels- alder reaction                                         Methyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic                acid                                                                                         ##STR92##                                                                    and                                                                            ##STR93##                                           Methylcrotonate (catalytic Diels- alder reaction)                                        Methyl ester of 1,3- and 3,5-dimethyl norbornane-2- carboxylic                acid                                                                                         ##STR94##                                                                    and                                                                            ##STR95##                                           Ethylcrotonate (catalytic Diels- alder reaction)                                         Ethyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic                 acid                                                                                         ##STR96##                                                                    and                                                                            ##STR97##                                           Ethylacrylate (catalytic Diels- alder reaction)                                          Ethyl ester of 1- and 5-methyl- 5-norbornene-2- carboxylic                    acid                                                                                         ##STR98##                                                                    and                                                                            ##STR99##                                           Ethylacrylate (catalytic Diels- alder reaction)                                          Ethyl ester of 1- and 5-methyl- norbornane-2- carboxylic                                     ##STR100##                                                                   and                                                                            ##STR101##                                          n-Butylacrylate (catalytic Diels- alder reaction)                                        n-Butyl ester of 1- and 5-methyl- 5-norbornene-2- carboxylic                  acid                                                                                         ##STR102##                                                                   and                                                                            ##STR103##                                          Ethyl- methacrylate (catalytic Diels- alder reaction)                                    Ethyl esters of 1,2- and 2,5-dimethyl- 5-norbornene-2-                        carboxylic acid                                                                              ##STR104##                                                                   and                                                                            ##STR105##                                          Ethylcrotonate (catalytic Diels- alder reaction)                                         Ethyl ester of 1,3- and 3,5-dimethyl- norbornane-2- carboxylic                acid                                                                                         ##STR106##                                                                   and                                                                            ##STR107##                                          Isopropylacrylate (thermal non- catalytic Diels- alder reaction)                         Isopropyl ester of 5- and 6-methyl-5- norbornane-2- carboxylic                acid                                                                                         ##STR108##                                                                   and                                                                            ##STR109##                                          Ethylacrylate                                                                            Ethyl esters of 1-; 4-; 5-; and 6-methyl- 5-norbornane-2-                     carboxylic acid                                                                              ##STR110##                                                                    ##STR111##                                                                    ##STR112##                                                                   and                                                                            ##STR113##                                          Ethylacrylate (thermal Diels- alder non-cataly- tic reaction)                            Ethyl ester of 1-; 4-; 5-; and 6-methyl- norbornane-2-                        carboxylic acid                                                                              ##STR114##                                                                    ##STR115##                                                                    ##STR116##                                                                   and                                                                            ##STR117##                                          Ethylcrotonate (non-catalytic thermal Diels- alder reaction)                             Ethyl esters of 3,5- and 3,6-dimethyl- 5-norbornane-2-                        carboxylic acid                                                                              ##STR118##                                                                   and                                                                            ##STR119##                                          ______________________________________                                    

                                      TABLE II                                    __________________________________________________________________________                                  Smoking                                         Reaction Product                                                                        Fragrance Food Flavor                                                                             Tobacco Flavor                                  Name      Properties                                                                              Properties                                                                              Properties                                      __________________________________________________________________________    Methyl ester of                                                                         A fruity, ba-                                                                           A burnt fruit                                                                           Sweet, fruity,                                  1,3- and 3,5-                                                                           nana, creamy                                                                            aroma and berry-like, woody                               dimethyl norbor-                                                                        aroma with                                                                              taste at 0.1                                                                            aroma prior to                                  nene-2-carboxylic                                                                       camphoraceous                                                                           ppm       smoking and a                                   acid      and minty           sweet, fruity                                   (catalytic Diels-                                                                       undertones          aroma on smoking                                alder reaction)               both in the main-                                                             and sidestreams                                 Methyl ester of                                                                         A fruity, cam-                                                                          A fruity and                                                                            Prior to smoking                                1,3- and 3,5-                                                                           phoraceous and                                                                          blackberry-                                                                             a sweet, woody,                                 dimethyl norbor-                                                                        herbaceous                                                                              like aroma and                                                                          spicy, cooling                                  nane-2-carboxylic                                                                       aroma     taste at 0.1                                                                            and clove-like                                  acid                ppm       aroma profile;                                  (catalytic Diels-             and on smoking                                  alder reaction)               a sweet, spicy,                                                               cooling and                                                                   woody aroma and                                                               taste in both                                                                 the main stream                                                               and the side                                                                  stream                                          Ethyl ester of                                                                          A sweet, spicy                                                                          A sweet, fruit,                                                                         A sweet, fruity,                                1,3- and 3,5-                                                                           herbal, woody,                                                                          berry-like,                                                                             berry, spicy,                                   dimethyl norbor-                                                                        eucalyptol-like                                                                         spicy, black                                                                            cinnamon bark-                                  nene-2-carboxylic                                                                       aroma profile                                                                           pepper-like,                                                                            like and clove-                                 acid      with a dis-                                                                             herbaceous,                                                                             like aroma and                                  (catalytic Diels-                                                                       tinct calamnus                                                                          clove-like                                                                              taste profile                                   alder reaction)                                                                         undertone with                                                                          aroma and prior to and on                                           tagett-like                                                                             taste profile                                                                           smoking in the                                            nuances on                                                                              at 10 ppm main stream and                                           dryout    causing it to                                                                           the side stream                                                     be useful in                                                                  blueberry,                                                                    tobacco, clove                                                                and raspberry                                                                 flavor food-                                                                  stuffs                                                    Ethyl ester of                                                                          A sweet, fruity                                                                         A sweet, fruity,                                                                        A fruity, banana-                               1- and 5-methyl-                                                                        (banana-like)                                                                           red berry-like,                                                                         like, green and                                 5-norbornene-2-                                                                         creamy and                                                                              raspberry and                                                                           strawberry-like                                 carboxylic acid                                                                         minty aroma                                                                             seedy aroma and                                                                         aroma and taste                                 (catalytic Diels-                                                                       profile with                                                                            taste profile                                                                           both prior to                                   alder reaction)                                                                         the minty with an addi-                                                                           and on smoking                                            notes outstand-                                                                         tional strawberry                                                                       in the main                                               ing on dryout                                                                           taste nuance at                                                                         stream and in                                                       0.02 ppm causing                                                                        the side stream                                                     it to be useful                                                               in red berry,                                                                 cherry, rasp-                                                                 berry and straw-                                                              berry flavors                                             Ethyl ester of                                                                          A fruity, bana-                                                                         A sweet, fruity,                                                                        A sweet, fruity,                                1- and 5-methyl-                                                                        an like, and                                                                            raspberry, ver-                                                                         "juicyfruit",                                   5-norbornane-2-                                                                         creamy aroma                                                                            mouth-like and                                                                          woody, piney,                                   carboxylic acid                                                                         profile   blueberry aroma                                                                         and blueberry                                   (catalytic Diels-   with fruit,                                                                             aroma and                                       alder reaction)     raspberry and                                                                           taste profile                                                       blueberry taste                                                                         prior to and                                                        characteristics                                                                         on smoking in                                                       at 0.01 ppm and                                                                         the mainstream                                                      at 1 ppm causing                                                                        and in the side                                                     it to be useful                                                                         stream                                                              for vermouth,                                                                 blueberry and                                                                 raspberry flavors                                                             and mouthwash and                                                             toothpaste                                                                    flavors                                                   n-Butyl ester of                                                                        A balsamic and                                                                          A fruity, straw-                                                                        An earthy,                                      1- and 5-methyl-                                                                        rum/butterscotch                                                                        berry, blueberry                                                                        mushroom aroma                                  5-norbornene-2-                                                                         aroma profile                                                                           and balsamic                                                                            prior to and                                    carboxylic acid     aroma profile                                                                           on smoking                                      (catalytic Diels-   with blueberry,                                           alder reaction)     balsamic and                                                                  bitter taste                                                                  characteristics                                                               at 2 ppm                                                  Ethyl esters of                                                                         A green, minty,                                                                         A fruit, rasp-                                                                          A sweet, green,                                 1,2- and 2,5-                                                                           borneol-like,                                                                           berry and seedy                                                                         herbaceous,                                     dimethyl-5-nor-                                                                         spicy, somewhat                                                                         aroma and taste                                                                         dill and fruity                                 bornene-2-carboxy-                                                                      medicinal aroma                                                                         profile with                                                                            aroma and taste                                 lic acid  profile remin-                                                                          additional                                                                              profile both                                    (catalytic Diels-                                                                       iscent of bitter taste                                                                            prior to and                                    alder reaction)                                                                         pepacuana boric                                                                         nuances at 0.2                                                                          on smoking in                                             extract   ppm       mainstream and                                                                in the side                                                                   stream                                          Ethyl esters of                                                                         A fruity, A fruity, blue-                                           1,3- and 3,5-                                                                           piney, herb-                                                                            berry and                                                 dimethyl-5-nor-                                                                         aceous and                                                                              herbaceous aroma                                          bornane-2-carboxy-                                                                      cassis aroma                                                                            character with a                                          lic acid  profile with                                                                            sweet, fruity                                             (catalytic Diels-                                                                       calamnus under-                                                                         and blueberry                                             alder reaction)                                                                         tones     flavor charact-                                                               eristic at                                                                    0.02 parts per                                                                million                                                   Isopropyl A green, fruity                                                                         A camphoraceous                                           ester of 5- and                                                                         aroma     blueberry and                                             6-methyl-5-nor-     wild strawberry                                           bornane-2-car-      aroma and flavor                                          boxylic acid        profile at 0.1                                            (thermal non-       ppm                                                       catalytic                                                                     Diels-alder                                                                   reaction)                                                                     Ethyl esters of                                                                         A sweet, fruity,                                                                        Sweet, fruity,                                                                          A fruity,                                       1-; 4-; 5-; and 6-                                                                      minty aroma                                                                             raspberry natural                                         methyl-5-nor-       aroma with                                                                              tobacco                                         bornane-2-car-      strawberry                                                                              aroma and                                       boxylic acid        nuances   taste both                                      (thermal non-                 prior to and                                    catalytic                     on smoking                                      Diels-alder                   in the main                                     reaction)                     stream and                                                                    the side                                                                      stream                                          Ethyl ester of                                                                          A fruity, banana                                                                        A raspberry                                                                             A sweet,                                        1-; 4-; 5-; and 6-                                                                      and creamy aroma                                                                        aroma and fruity "juicy-                                  methyl-nor-                                                                             profile   taste with                                                                              fruit" aroma                                    bornane-2-car-      blueberry and taste                                       boxylic acid        nuances at                                                                              profile both                                    (thermal non-       0.05 ppm  prior to and                                    catalytic                     on smoking                                      Diels-alder                   in the main                                     reaction)                     stream and in                                                                 the side                                                                      stream                                          Ethyl esters of                                                                         An intense,                                                                             A sweet, fruity,                                                                        A sweet,                                        3,5- and 3,6-                                                                           fruity, straw-                                                                          clove-like aroma                                                                        fruity, spicy                                   dimethyl- berry-like,                                                                             and taste pro-                                                                          clove-like                                      5-norbornane-2-                                                                         raspberry-like,                                                                         file at 4 ppm                                                                           aroma and                                       carboxylic acid                                                                         roseda body-        taste both                                      (thermal non-                                                                           like aroma but      prior to and                                    catalytic does not have       on smoking                                      Diels-alder                                                                             tagett nuances      in the main                                     reaction)                     stream and                                                                    the side                                                                      stream                                          __________________________________________________________________________

When the norbornane derivatives of our invention are used as food flavoradjuvants, the nature of the co-ingredients included with each of thesaid norbornane derivatives in formulating the product composition willalso serve to alter, modify, augment or enhance the organolepticcharacteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually to, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers ofsoftening agents, e.g., glycerine; and a flavor composition whichincorporates one or more of the norbornane derivatives of our invention,and in addition, sweetening agents which may be sugars, includingsucrose or dextrose and/or artificial sweeteners such as cyclamates orsaccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents includes emulsifying agents, e.g., fatty acidssuch as capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar the the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include aldehydes, esters,natural oils, alcohols, sulfides, ketones, lactones, carboxylic acidsand hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde,anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate,cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol,acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil,limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde,cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin,maltol, parahydroxybenzyl acetate, dimethyl sulfide, alphaionone, aceticacid, isobutyl acetate, acetone, butyric acid, formic acid, valericacid, amyl acetate, amyl butyrate, anethol, benzyl salicylate, diacetyl,dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate,ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenylbutyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, betaionone,isobutyl cinnamate, jasmine, lemon essential oil, methyl butyrate,methyl caproate, methyl disulfide, methyl p-naphthyl ketone, orrisbutter, rose absolute, terpenyl acetate, gamma-undecalactone, vanillaand alcohol.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the norbornane derivatives ofour invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be non-reactive with the norbornanederivatives of our invention and (iii) be capable of providing anenvironment in which the norbornane derivatives can be dispersed oradmixed to provide a homogeneous medium. In addition, selection of oneor more flavoring adjuvants, as well as the quantities thereof willdepend upon the precise organoleptic character desired in the finishedproduct. Thus, in the case of flavoring compositions, ingredientselection will vary in accordance with the foodstuff, chewing gum,medicinal product or toothpaste to which the flavor and/or aroma are tobe imparted, modified, altered or enhanced. In contradistinction, in thepreparation of solid products, e.g., simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofnorbornane derivatives employed in a particular instance can vary over arelatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected to be effective, i.e., sufficient to alter, modify,or enhance the organoleptic characteristics of the parent composition,whether foodstuff per se, chewing gum, per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of norbornane derivatives will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and, in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of norbornane derivativesranging from a small but effective amount, e.g., 0.01 parts per millionup to about 100 parts per million based on total composition aresuitable. Concentrations in excess of the maximum quantity stated arenot normally recommended, since they fail to prove commensurateenhancement of organoleptic properties. In those instances, wherein thenorbornane derivatives are added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective norbornane derivative concentration in the foodstuffproduct.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the norbornane derivatives inconcentrations ranging from about 0.01% up to about 15% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the norbornane derivatives with, forexample, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Preprepared flavor mixes in powder form e.g.,a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and norbornane derivativesin a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the norbornane derivatives ofour invention, the following adjuvants:

Heliotropin;

Terpinenol-4;

Benzaldehyde;

Anisaldehyde;

Phenylacetaldehyde;

Benzyl formate;

Benzyl acetate;

Cis-3-hexenyl benzoate;

Methyl hexanoate;

Hexanal;

Eucalyptol;

Eugenol;

Acetaldehyde;

Ethyl acetate;

Ethyl butyrate;

Turpentine gum oil;

Limonene;

Gum camphor;

Isobornyl acetate;

Borneol;

Cinnamic aldehyde;

Cuminic aldehyde;

Furfural;

Methyl cinnamate;

Cassia oil;

Vanillin;

Malto;

Paranydroxybenzylacetone;

Dimethyl sulfide;

Alpha-ionone;

Acetic acid;

Isobutyl acetate;

Acetone;

Butyric acid;

Formic acid;

Valeric acid;

Amyl acetate;

Amyl butyrate;

Anethol;

Benzyl salicylate;

Diacetyl;

Dimethyl anthranilate;

Ethyl methylphenylglycidate;

Ethyl succinate;

Ethyl valerate;

Geraniol;

Cis-3-hexen-1-ol;

2-Hexenyl acetate;

2-Hexenyl butyrate;

Hexyl butyrate;

4-(p-Hydroxyphenyl)-2-butanone;

Beta-ionone;

Isobutyl cinnamate;

Jasmine;

Lemon essential oil;

Methyl butyrate;

Methyl capronate;

Methyl disulfide;

Methyl p-naphthyl ketone;

Orris butter;

Rose absolute

Terpenyl acetate;

Gamma-undecalactone;

Vanilla; and

Alcohol.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which desired spicy, cooling, clove-like, cinnamonbark-like, sweet, fruity, berry-like, juicyfruit, woody, piney,blueberry, banana, green, herbaceous, strawberry-like, and dill flavorcharacteristics of natural tobacco (prior to smoking and, on smoking, inthe mainstream and in the sidestream) as well as cooling effects, arecreated or enhanced or modified or augmented and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable natural aromatic tobacco flavoringcharacteristics with spicy, cooling, clove-like, cinnamon bark-like,sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana,green, herbaceous, strawberry-like and dill notes may be imparted tosmoking tobacco products and may be readily varied and controlled toproduce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore norbornane derivatives of our invention.

In addition to the norbornane derivatives of our invention otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with thenorbornane derivatives as follows:

I. Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b-)furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more norbornanederivatives of our invention and, if desired, one or more of the aboveindicated additional flavoring additives may be added to the smokingtobacco material, to the filter or to the leaf or paper wrapper. Thesmoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of spicy and/or cooling and/orclove-like and/or cinnamon bark-like and/or sweet and/or fruity and/orberry-like and/or juicyfruit and/or woody and/or piney and/or blueberryand/or banana and/or green and/or herbaceous and/or strawberry-likeand/or dill notes, we have found that satisfactory results are obtainedif the proportion by weight of the sum total of norbornane derivative(s)to smoking tobacco material is between 50 ppm and 1,500 ppm(0.015%-0.15%). We have further found that satisfactory results areobtained if the proportions by weight of the sum total of norbornanederivative used to flavoring material is between 1,500 and 15,000 ppm(0.15%-1.5%).

Any convenient method for incorporating the norbornane derivative(s)into the tobacco product may be employed. Thus, the norbornanederivative(s) taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, diethyl ether and/orvolative organic solvents and the resulting solution may either bespread on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of the norbornane derivative(s) taken alone or taken furthertogether with other flavoring additives as set forth above, may beapplied by means of a suitable applicator such as a brush or roller onthe paper or leaf wrapper for the smoking product, or it may be appliedto the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated by have the norbornanederivative(s) in excess of the amounts or concentrations above indicatedso that when blended with other tobaccos, the final product will havethe precentage within the indicated range.

In accordance with one specific example of our invention an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethanolsolution of the mixture of 1,3- and 3,5-dimethyl-2-norbornane carboxylicacid methyl esters having the structures: ##STR120## in an amount ofmixture to provide tobacco composition containing 800 ppm by weight ofthe mixture of the two esters on a dry basis. Thereafter the alcohol isremoved by evaporation and the tobacco is manufactured into cigarettesby the usual techniques. The cigarette when treated as indicated has adesired and pleasing aroma which is detectable in the mainstream and thesidestream when the cigarette is smoked. This aroma is described asbeing sweeter, more aromatic, more tobacco-like having sweet, spicy,cooling, woody and clove-like notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products, formed from sheeted tobacco dust or fines mayalso be used. Likewise, the norbornane derivative(s) of our inventioncan be incorporated with materials such as filter tip materials (e.g.cellulose acetate filters wherein spicy, cooling, clove-like, cinnamonbark-like, sweet, fruity, berry-like, juicyfruit, woody, piney,blueberry, banana, green, herbaceous, strawberry-like and/or dilleffects are desired), seam paste, packaging materials and the like whichare used along with tobacco to form a product adapted for smoking.Furthermore, the norbornane derivative(s) can be added to certaintobacco substitutes of natural or synthetic origin (e.g., dried lettuceleaves) and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

The norbornane derivative(s) and one or more auxiliary perfumeingredients, including, for example, hydrocarbons, alcohols, ketones,aldehydes, nitriles, esters, lactones or cyclic esters, syntheticessential oils and natural essential oils, may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance, particularly and preferably in fruity, banana,creamy, camphoraceous, herbaceous, strawberry-like, raspberry-like,reseda body-like, sweet, spicy, woody, eucalyptol-like, tagett-like,rum/butterscotch, balsamic, green, and/or minty fragrances. Such perfumecompositions usually contain (a) the main note or the "bouquet: orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low boiling fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the norbornane derivative(s) of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of norbornane derivative(s) of our invention which will beeffective in perfume compositions as well as perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of norbornanederivative(s) or even less (e.g., 0.005%) can be used to impart afruity, banana, creamy, camphoraceous, strawberry-like, raspberry-like,reseda body-like, herbaceous, sweet, spicy, woody, eucalyptol-like,rum/butterscotch, balsamic, green, minty, borneol-like, tagett-likeand/or medicinal odor with camphor, minty and calamnus-like nuances tosoaps, detergents (including anionic, nonionic, cationic andzwitterionic solid or liquid detergents), cosmetics, fabric softeners,dryer-added fabric softener articles, fabric whiteners and opticalbrighteners or other products. The amount employed can range up to 70%of the fragrance components and will depend on considerations of cost,nature of the end product, the effect desired on the finished productand the particular fragrance sought.

The norbornane derivative(s) of our invention are useful (taken alone ortogether with other ingredients in perfume compositions) in detergentsand soaps, space odorants and deodorants, perfumes, colognes, toiletwater, bath preparations, such as lacquers, brilliantines, pomades andshampoos; cosmetic preparations, such as creams, deodorants, handlotions and sun screens; powders such as talcs, dusting powders, facepowders and the like. As little of 0.005% of the norbornanederivative(s) (in the ultimate perfumed article) will suffice to impartan intense, fruity, banana, creamy, camphoraceous, strawberry-like,raspberry-like, reseda body-like, herbaceous, sweet, spicy, woody,eucalyptol-like, rum/butterscotch, balsamic, green, minty, borneol-like,tagett-like and/or medicinal note to various types of perfumed articles.Generally no more than 3% of the norbornane derivative(s) based on theultimate end product (perfumed article) is required.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the norbornanederivative(s). The vehicle can be a liquid such as a non-toxic alcohol,a non-toxic glycol or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic), or components for encapsulatingthe composition (such as gelatin).

It will thus be apparent that the norbornane derivative(s) of ourinvention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

The following examples serve to illustrate processes for specificallyproducing the norbornane derivative(s) useful in our invention.

The following examples also serve to illustrate specific embodiments ofour invention.

It will be understood that these examples are illustrative and theinvention is to be considered to be restricted thereto only as indicatedin the appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of 1,3-Dimethyl-5-Norbornene-2-Carboxylic AcidMethyl Ester and 3,5-Dimethyl-5-Norbornene-2-Carboxylic Acid MethylEster (Catalytic Diels-Alder Reaction)

Reaction: ##STR121##

Into a 3 liter flask equipped with stirrer, thermometer, condenser,addition funnel and cooling bath are charged 1000 ml toluene, 500 gramsmethyl crotonate, 45 grams ethyl aluminum dichloride. The resultingmixture is cooled to 20°-25° C. Over a period of 50 minutes whilemaintaining the reaction mass at 24°-25° C., 320 grams of methylcyclopentadiene (mixture of 1-methyl-1,3-cyclopentadiene and2-methyl-1,3-cyclopentadiene (50% in toluene solution)) is added. Afterthe completion of the addition of the methyl cyclopentadiene mixture,the reaction mass is stirred for a period of 3 hours at 21°-25° C. Atthe end of the three hour period the reaction mass is heated to 40° C.and the temperature is maintained at 40° C. for a period of 2.7 hours.At the end of the 2.7 hour period the reaction mass is cooled to 20° C.and is poured into one liter of 10% hydrochloric acid solution. Thereaction mass now exists in two phases. The aqueous phase is separatedfrom the organic phase. The aqueous phase is extracted with 500 mltoluene. The toluene extract and organic phase are combined. Theresulting organic phase is then washed as follows:

One 1 liter portion water;

One 1 liter portion saturated sodium carbonate;

One 1 liter portion water.

The toluene is then removed under reduced pressure. The resultingorganic material is then distilled in a 12 inch Goodloe column yieldingthe following fractions:

    ______________________________________                                                Vapor   Liqiud                 Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg.  Reflux                                                                              Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                              Ratio (g.)                                   ______________________________________                                        1       41/43   70/71    2.1/2.0 9:1   21.0                                   2       48      72       2.0     9:1   22.6                                   3       45      73       2.0     9:1   21.8                                   4       48      73       2.0     9:1   22.2                                   5       48      72       2.0     9:1   16.7                                   6       48      73       2.0     9:1   22.0                                   7       49      74       2.0     9:1   19.9                                   8       49      86       2.0     9:1   20.5                                   9       50/35    95/205  2.5/1.0 9:1   12.0                                   ______________________________________                                    

Fractions 4-7 are bulked for purposes of flavor evaluation. The bulkedfractions 4-7 as analyzed by NMR, IR and mass spectral analysis containa mixture of compounds having the structures: ##STR122## Fractions 4-7bulked has a burnt fruit aroma and flavor characteristic at 0.1 ppm.

Fractions 4-7 bulked has a fruity, banana, creamy aroma withcamphoraceous, minty undertones.

FIG. 1 represents the GLC profile for the reaction product of Example Icontaining the compounds having the structures: ##STR123##

FIG. 2A represents the NMR spectrum for fraction 8 of the foregoingdistillation containing only the compound having the structure:##STR124##

FIG. 2B represents the NMR spectrum for fraction 2 of the foregoingdistillation containing the compound having the structure: ##STR125##

FIG. 3A represents the infrared spectrum for fraction 8 of the foregoingdistillation containing only the compound having the structure:##STR126##

FIG. 3B represents the infrared spectrum for fraction 2 of the foregoingdistillation containing only the compound having the structure:##STR127##

FIG. 4 represents the mass spectrum for the reaction product of ExampleI containing the compounds having the structures: ##STR128##

EXAMPLE II Preparation of 1,3-Dimethyl-5-Norbornane-2-Carboxylic AcidMethyl Ester and 3,5-Dimethyl-5-Norbornane-2-Carboxylic Acid MethylEster

Reaction: ##STR129##

Into a 500 ml pressure bottle held in a Parr shaker is charged 100 mlisopropyl alcohol and 160 grams (0.89 moles) of the methylcyclopentadiene/methyl crotonate adduct having the structures:##STR130## prepared according to Example I and 4 grams of Raney Nickel.The Parr shaker is purged with hydrogen and charged to 50 psig. Shakingis begun and the Parr shaker is recharged with hydrogen when necessaryin order to maintain the pressure at 50 psig. A total pressure drop of74 pounds of hydrogen is observed. A GLC profile (conditions: Carbowaxcolumn programmed at 80°-220° C. at 8° C. per minute) indicates somechange. NMR analysis indicates that all of the olefin is consumed.

At the end of the reaction the pressure bottle is opened and the RaneyNickel catalyst is filtered and the solvent is stripped off underreduced pressure. The resulting residue is distilled yielding 122 gramsof product. The distillation takes place on a 12"×2' Goodloe columnyielding the following fractions:

    ______________________________________                                                Vapor   Liquid                 Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg.  Reflux                                                                              Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                              Ratio (g.)                                   ______________________________________                                        1       37/41   72/75    .65/.8  9:1   21                                     2       42      76        .65    9:1   25                                     3       43      78        .65    9:1   23                                     4       44      80       .8      9:1   19                                     5       45      95       .8      9:1   22                                     6       60      215      .8      9:1   12                                     ______________________________________                                    

NMR, mass spectral and IR analysis yields the information that theresulting product is a mixture of the compounds having the structures:##STR131##

FIG. 5 sets forth the GLC profile for the reaction product producedaccording to this example. FIG. 6A sets forth the NMR spectrum for peak1 of the GLC profile which consists essentially of the compound havingthe structure: ##STR132## FIG. 6B sets forth the NMR spectrum forfraction 6 of the foregoing distillation which consists essentially ofthe compound having the structure: ##STR133## FIG. 7A sets forth theinfrared spectrum for peak 1 of the foregoing GLC profile which consistsessentially of the compound having the structure: ##STR134## FIG. 7Bsets forth the infrared spectrum for fraction 6 of the foregoingdistillation which consists essentially of the compound having thestructure: ##STR135## FIG. 8 sets forth a mass spectrum for the reactionproduct of this example which contains the compounds having thestructures: ##STR136##

The resulting mixture, from a food flavor standpoint, has a fruity,blueberry aroma and flavor characteristic at 0.1 ppm. The resultingmixture from a fragrance standpoint, has a fruit, camphoraceous andherbaceous aroma profile.

The mixture of this example also has a sweet, woody, spicy, cooling andclove-like aroma profile prior to smoking and a sweet, spicy, coolingand woody aroma and taste profile on smoking tobacco articles in boththe mainstream and the sidestream.

EXAMPLE III Preparation of the Ethyl Ester of 1,3 and 3,5-Dimethyl5-Norbornene Carboxylic Acid (Catalytic Diels-Alder Reaction)

Reaction: ##STR137##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,condenser, addition funnel, nitrogen purge and cooling bath are added1000 ml toluene; 600 grams ethyl crotonate; and 50 grams of a 25%solution of ethyl aluminum dichloride in anhydrous toluene. Theresulting mixture is cooled to 20°-25° C. and over a period of 3 hourswhile maintaining the temperature of the reaction at 20°-23° C., 378grams of methyl cyclopentadiene mixture containing compounds having thestructures: ##STR138## are added.

The reaction mass is then poured into one liter of a 10% aqueoushydrochloric acid solution. The reaction mass now exists in two phases;an aqueous phase and an organic phase. The aqueous phase is removed fromthe organic phase and the aqueous phase is extract with one 500 mlvolume of toluene. The toluene and organic phases are combined andwashed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium bicarbonate solution; and

C. One 1 liter portion of water.

The solvent is stripped off via vacuum. The resulting material is thendistilled using a 12 inch Goodloe column yielding the followingfractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.   mm/Hg.  Reflux                                                                              Fraction                                No.    (°C.)                                                                           (°C.)                                                                          Pressure                                                                              Ratio (g.)                                    ______________________________________                                        1      32       53      2.0     9:1   43.8                                    2      30       62      1.0     9:1   43.0                                    3      38       73      1.8     9:1   38.3                                    4      40       73      .86     9:1   37.5                                    5      44       74      .86     9:1   44.5                                    6      44       76      .86     9:1   37.0                                    7      44       82      .86     9:1   52.7                                    8      44       90      .86     9:1   43.6                                    9      44       102     .85     9:1   48.7                                    10     55       130     .85     9:1   16.2                                    11     65       220     2.5     9:1   48.8                                    ______________________________________                                    

NMR, IR and mass spectral analysis yields the information that thereaction product contains compounds having the structures: ##STR139##

FIG. 9 sets forth the GLC profile prior to distillation of the resultingreaction product.

FIG. 10A sets forth the NMR spectrum for fraction 10 of the foregoingdistillation containing only the product having the structure:##STR140##

FIG. 10B is the NMR spectrum for the compound contained in fraction 6 ofthe foregoing distillation, having the structure: ##STR141##

FIG. 11A is the infrared spectrum for the compound of fraction 10 of theforegoing distillation having the structure: ##STR142##

FIG. 11B is the infrared spectrum for the compound contained in fraction6 of the foregoing distillation, having the structure: ##STR143##

FIG. 12 is the mass spectrum for the mixture of compounds produced bythe foregoing reaction having the structures: ##STR144##

Bulked fractions 5-11 containing the compounds having the structures:##STR145## from a fragrance standpoint has a sweet, spicy, herbal,woody, eucalyptol-like aroma with distinct calamnus undertones.

Bulked fractions 5-11 from a food flavor standpoint has a sweet, fruity,berry-like, spicy, black pepper-like, herbaceous and clove-like aromaand taste profile at 10 ppm causing said bulked fractions to be usefulin blueberry flavored tobacco (cloves) flavor and raspberry flavor.

Bulked fractions 5-11 from a tobacco flavor standpoint has a sweet,fruity, berry, spicy, cinnamon bark-like and clove-like aroma and tasteprofile both prior to and on smoking in the mainstream and in thesidestream of smoking tobacco articles such as cigarettes and cigars.

EXAMPLE IV Preparation of Ethyl Esters of 1- and5-Methyl-5-Norbornene-2-Carboxylic Acids (Catalytic Diels-AlderReaction)

Reaction: ##STR146##

Into a three liter flask equipped with thermometer, stirrer, condenser,addition funnel, cooling bath and nitrogen purge are placed one gram ofhydroquinone, 1000 ml toluene and 50 grams of 25% ethyl aluminumdichloride dissolved in anhydrous toluene. The reaction mass is cooledto about 10° C. and, over a period of 30 minutes, 600 grams of ethylacrylate is added to the resulting mixture. During the addition thetemperature of the mixture is maintained at between 10° C. and 14° C.

Over a period of three hours while maintaining the reaction temperatureat 20°-23° C., 389 grams of a mixture of 1-methyl-1,3-cyclopentadieneand 2-methyl-1,3-cyclopentadiene is added to the reaction mixture. Atthe end of the three hour period GLC analysis indicates the reaction tobe complete.

The resulting reaction mass is poured into one liter of 10% aqueoushydrochloric acid. The reaction mass now exists in two phases; anorganic phase and an aqueous phase. The aqueous phase is separated fromthe organic phase and the organic phase is washed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium bicarbonate solution;

C. One 1 liter portion of water;

D. One 1 liter portion of water.

The pH of the resulting washing is about six.

The resulting organic layers are combined and the toluene is strippedoff under vacuum. Calcium carbonate and primol® is added to the reactionmass and the reaction mass is distilled yielding the following fractionson a 12 inch Goodloe column:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    mm/Hg. Reflux Fraction                               No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             Ratio  (g.)                                   ______________________________________                                        1      48/48    63/65    3.0/3.0                                                                              9:1    23.8                                   2      50       64       3.0    9:1    19.3                                   3      50       64       2.8    9:1    20.5                                   4      53       64       2.6    9:1    19.1                                   5      54       64       2.6    9:1    20.2                                   6      55       65       2.8    9:1    19.9                                   7      56       66       2.7    9:1    25.2                                   8      54       66       2.5    9:1    21.7                                   9      54       66       2.5    9:1    48.6                                   10     54       66       2.5    9:1    55.8                                   11     54       67       2.5    9:1    48.7                                   12     57       77       2.5    9:1    59.7                                   13     57       77       2.5    9:1    47.2                                   14     57       87       2.5    9:1    58.0                                   15     55/58     87/108  2.5/2.5                                                                              4:1    33.0                                   16     45       110      3.0    4:1     6.6                                   ______________________________________                                    

Fractions 7-12 are bulked and NMR, IR and mass spectral analysis yieldthe information that these fractions consist essentially of a mixture ofcompounds having the structures: ##STR147##

FIG. 13 is the GLC profile of the crude reaction product washed, butbefore distilling. (Conditions: Carbowax column programmed at 80°-122°C. at 8° C. per minute).

FIG. 14 is the GLC profile of fractions 7-12 from the foregoingdistillation, bulked.

FIG. 15A is the NMR spectrum for the compound having the structure:##STR148##

FIG. 15B is the NMR spectrum for the compound having the structure:##STR149##

FIG. 16A is the infrared spectrum for the compound having the structure:##STR150##

FIG. 16B is the infrared spectrum for the compound having the structure:##STR151##

FIG. 17 is the mass spectrum for the mixture of compounds having thestructures: ##STR152##

The mixture of compounds having the structures: ##STR153## from afragrance standpoint has a sweet, fruity (banana-like) and creamy aromaprofile with minty nuances intense on dryout.

From a food flavor standpoint, the resulting mixture has a sweet,fruity, red berry, raspberry and seedy aroma and taste and in addition astrawberry taste at 0.02 ppm. Thus, this material is useful in redberry, cherry, raspberry and strawberry flavored foodstuffs.

The resulting mixture has a fruity, banana, green and strawberry-likearoma and taste both prior to and on smoking smoking tobacco articles inboth the mainstream and the sidestream.

EXAMPLE V Preparation of the Ethyl Esters of 1- and 5-Methylnorbornane-2-Carboxylic Acids

Reaction: ##STR154##

Into a 500 ml pressure bottle attached to a Parr shaker is charged 200grams (1.11 moles) of the reaction mixture (bulked fractions 7-12)produced according to Example IV consisting essentially of compoundshaving the structures: ##STR155## 5 grams of Raney Nickel and 125 ml ofisopropyl alcohol. The Parr shaker apparatus is purged six times withhydrogen and the 500 ml pressure bottle with contents is pressurized to50 psig. The bottle is closed and shaking is begun and continued untilthe hydrogen uptake ceases. This period of time takes 4.25 hours. The500 ml pressure bottle is recharged when necessary. At the end of thereaction the 500 ml pressure bottle is opened and the reaction mass isfiltered and the solvent stripped in vacuum. The resulting residue isdistilled on a 1' Goodloe-silver column and yields the followingfractions:

    ______________________________________                                               Vapor   Liquid                  Weight of                              Fraction                                                                             Temp.   Temp.    mm/Hg.  Reflux Fraction                               No.    (°C.)                                                                          (°C.)                                                                           Pressure                                                                              Ratio  (g.)                                   ______________________________________                                        1       54/42  77/77    2.8/.8  9:1    18.5                                   2      42      77       0.75    9:1    22.2                                   3      42      78       0.70    9:1    22.0                                   4      46      85       0.70    9:1    23.0                                   5      50      87       1.4     9:1    18.0                                   6      50      90       0.8     9:1    21.0                                   7      51      111      0.7     9:1    19.0                                   8      45      170      0.75    9:1    23.0                                   9      39      214      0.76    9:1    3.0                                    ______________________________________                                    

NMR, IR and mass spectral analysis on fractions 1 and 9 yield theinformation that the resulting mixture contains and consists essentiallyof the compounds having the structures: ##STR156##

FIG. 18 is the GLC profile for the resulting reaction mixture.

FIG. 19A is the NMR spectrum for fraction 9 of the foregoingdistillation containing and consisting of the compound having thestructure: ##STR157##

FIG. 19B is the NMR spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR158##

FIG. 20A is the infrared spectrum for fraction 9 of the foregoingdistillation consisting of the compound having the structure: ##STR159##

FIG. 20B is the infrared spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR160##

FIG. 21 is the mass spectrum for the reaction product produced accordingto this example containing the mixture of compounds having thestructures: ##STR161##

From a fragrance standpoint bulked fractions 6-8 have a fruity, banana,and creamy aroma profile.

From a food flavor standpoint, bulked fractions 6-8 have a sweet,fruity, raspberry, vermount-like and blueberry aroma profile with afruity, raspberry and blueberry taste profile at 0.01 ppm and at 1 ppmcausing this mixture to be useful for vermouth, blueberry, raspberrymouthwash and toothpaste flavors.

From a tobacco flavor standpoint, bulked fractions 6-8 has prior to andon smoking in the mainstream and in the sidestream a sweet, fruity,"juicyfruit", woody, piney and blueberry aroma and taste profile.

EXAMPLE VI Preparation of 1- and 5-Methyl-5-Norbornene-2-Carboxylic Acidn-Butyl Esters (Catalytic Diels-Alder Reaction)

Reaction: ##STR162##

Into a 3 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, dropping funnel and cooling bath is placed 700 ml toluene and60 grams of ethyl aluminum dichloride. While maintaining the temperatureof the mixture at 20°-25° C., via the dropping funnel is added 300 gramsof n-butyl acrylate over a period of 20 minutes.

While keeping temperature at 20°-25° C. over a 40 minute period, 380grams of a 50% solution of 1-methyl-1,3-cyclopentadiene and2-methyl-1,3-cyclopentadiene is added to the reaction mass.

After about 2 hours an additional 30 grams of ethyl aluminum dichlorideis added and the reaction mass is stirred for another 1.5 hours whilemaintaining the temperature thereof at 20°-25° C.

Reaction mass is then added to 1 liter of 10% hydrochloric acid. Thereaction mass now exists in two phases; an organic phase and an aqueousphase. The organic phase is removed and washed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium carbonate;

C. One 1 liter portion of water.

The solvent is then removed by vacuum distillation and the resultingproduct is distilled on a 12" Goodloe column yielding the followingfractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.    mm/Hg. Reflux                                                                              Fraction                                No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             Ratio (g.)                                    ______________________________________                                        1      70/70    107/113  1.0/1.0                                                                              9:1/4:1                                                                             16.0                                    2      70       113      1.0    4:1   18.0                                    3      69       112      1.0    4:1   14.2                                    4      69       113      1.0    9:1   22.6                                    5      71       116      1.0    9:1   23.4                                    6      71       116      1.0    9:1   21.4                                    7      74       116      1.0    9:1   8.7                                     8      72       121      1.2    9:1   17.4                                    9      73       122      1.5    9:1   18.5                                    10     74       123      1.2    9:1   18.6                                    11     74       123      1.2    9:1   22.6                                    12     82       130      1.3    9:1   18.1                                    13     82       133      1.3    9:1   21.2                                    14     82       138      1.3    9:1   22.5                                    15     82       140      1.4    9:1   20.3                                    16     82       148      1.4    9:1   25.6                                    17     82       182      1.2    9:1   23.7                                    18     84       190      1.2    9:1   6.0                                     ______________________________________                                    

NMR, IR and mass spectral analysis yielding the information that theresulting product is a mixture of compounds having the structures:##STR163##

FIG. 22 sets forth the GLC profile for the reaction product.

FIG. 23A sets forth the NMR spectrum for fraction 14 for the foregoingfractional distillation and this fraction consists of compound havingthe structure: ##STR164##

FIG. 23B sets forth the NMR spectrum for fraction 4 of the foregoingdistillation consisting of the compound having the structure: ##STR165##

FIG. 24A sets forth the infrared spectrum for fraction 14 of theforegoing distillation consisting of the compound having the structure:##STR166##

FIG. 24B sets forth the infrared spectrum for fraction 4 of theforegoing distillation consisting of the compound having the structure:##STR167##

FIG. 25 sets forth the mass spectrum for the reaction product containingthe compounds having the structures: ##STR168##

From a fragrance standpoint bulked fractions 2-18 have a balsamic andrum/butterscotch aroma profile.

From a food flavor standpoint, bulked fractions 5-14 have a fruity,strawberry, blueberry, balsamic aroma profile with a blueberry, balsamicand bitter flavor profile at 2 ppm.

From a tobacco flavor standpoint, bulked fractions 5-14 have an earthyand mushroom aroma and taste both prior to and on smoking in themainstream and in the sidestream.

EXAMPLE VII Preparation of Ethyl Esters of 1,2- and2,5-Dimethyl-5-Norbornene-2-Carboxylic Acids (Catalytic Diels-AlderReaction)

Reaction: ##STR169##

Into a 5 liter flask equipped with condenser, thermometer, additionfunnel, nitrogen purge and cooling bath are placed 1000 ml toluene, 50grams of ethyl aluminum dichloride and 680 grams of ethyl methacrylate.The resulting mixture is cooled to 20°-25° C. and over a period of 3hours while maintaining the temperature at 23°-24° C. 400 grams of amixture of 1-methyl-1,3-cyclopentadiene and 2-methyl-1,3-cyclopentadieneis added to the reaction mass.

The reaction mass is then poured into 1 liter of 10% aqueoushydrochloric acid. The reaction mass now exists in two phases; anaqueous phase and an organic phase. The aqueous phase is extracted withone 500 ml portion of toluene and the toluene extract is combined withthe organic layer. The resulting organic phase is washed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium bicarbonate;

C. One 1 liter portion of water.

The resulting product is then stripped of solvent under vacuum. Primol®and Ionox® are then added to the reaction mass. The reaction mass isthen distilled on an 18" Goodloe column yielding the followingfractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.    mm/Hg. Reflux                                                                              Fraction                                No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             Ratio (g.)                                    ______________________________________                                        1      55/56    84/85    5.5/5.5                                                                              9:1   8.3                                     2      60       83       4.0    9:1   41.9                                    3      66       84       4.0    9:1   40.0                                    4      67       85       4.0    9:1   44.4                                    5      67       88       4.0    9:1   40.8                                    6      67       93       4.0    9:1   40.7                                    7      68       101      4.0    9:1   39.1                                    8      69       110      4.0    9:1   51.3                                    9      70       125      4.0    9:1   39.4                                    10     70       157      4.0    9:1   16.0                                    11     72/75    170/220  4.0/4.0                                                                              9:1   10.0                                    ______________________________________                                    

NMR, IR and mass spectral analysis yield the information that theresulting product contains two compounds having the structures:##STR170##

These materials are not separable via ordinary commercial physicalseparation procedures or commercial unit operations.

FIG. 26 sets forth the GLC profile for the resulting mixture containingthe compounds having the structures: ##STR171##

FIG. 27 sets forth the NMR spectrum for the mixture of compounds havingthe structures: ##STR172##

FIG. 28 sets forth the infrared spectrum for the compounds having thestructures: ##STR173## in admixture.

FIG. 29 sets forth the mass spectrum for the reaction product asproduced above containing and consisting of the structures: ##STR174##

Bulked fractions 4-10 from a fragrance standpoint has a green, minty,spicy aroma with medicinal nuances and a pepacuana bark extract typeundertone.

From a food flavor standpoint the resulting mixture containing thecompounds having the structures: ##STR175## has a fruity, raspberry andseedy aroma and flavor characteristic with additional bitter flavornuance at 0.2 ppm.

From a tobacco flavor standpoint, the resulting mixture has a sweet,green, herbaceous, dill and fruity aroma and taste both prior to and onsmoking in smoking tobacco in the main stream and in the side stream.

EXAMPLE VII-A Preparation of 1,3-and 3,5-Dimethyl Norbornane CarboxylicAcid Esters

Reaction: ##STR176##

Into a 500 ml pressure bottle equipped with Parr shaker is placed 200grams of the reaction product of Example III containing the compoundhaving the structures: ##STR177## 100 ml isopropyl alcohol and 5 gramsof Raney nickel. The 500 ml pressure bottle is then closed and placedunder hydrogen pressure. The Parr shaker is shaken under whilemaintaining the hydrogen pressure at 50 psig for a period of 5.5 hoursat a temperature of 20°-30° C. The Parr shaker and pressure bottleapparatus is then opened and the reaction mass is filtered and thesolvent is removed from the reaction mass. The resulting reactionproduct is then distilled yielding the following fractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.   mm. Hg. Reflux                                                                              Fraction                                No.    (°C.)                                                                           (°C.)                                                                          Pressure                                                                              Ratio (g.)                                    ______________________________________                                        1      53/55    70/73    1.2/1.2                                                                              9:1/9:1                                                                             5.7                                     2      55       73       1.2    3:1   18.5                                    3      54       73       1.2    3:1   15.9                                    4      57       74       1.2    3:1   13.0                                    5      58       74       1.2    3:1   17.3                                    6      62       75       1.2    3:1   14.6                                    7      64       75       1.5    3:1   25.3                                    8      60       80       1.4    3:1   17.6                                    9      58       78       1.2    3:1   24.9                                    10     59       80       1.2    3:1   18.5                                    11     59       82       1.2    3:1                                           ______________________________________                                    

Fractions 3-8 are bulked and NMR, IR and mass spectral analyses yieldthe information that bulked fractions 3-8 consist of the compoundshaving the structures: ##STR178##

Fraction 1 of the foregoing distillation contains the pure compoundhaving the structure: ##STR179##

Peak 2 of the foregoing GLC analysis consists of the compound having thestructure: ##STR180##

FIG. 31-A is the NMR spectrum for the compound having the structure:##STR181## of fraction 1 of the foregoing distillation.

FIG. 31-B is the NMR spectrum for the compound having the structure:##STR182## of peak 2 of the foregoing GLC profile.

FIG. 32-A is the infrared spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR183##

FIG. 32-B is the infrared spectrum for peak 2 of the foregoing GLCprofile consisting of the compound having the structure: ##STR184##

FIG. 33-A is the mass spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR185##

FIG. 33-B is the mass spectrum for peak 2 of the foregoing GLC profileconsisting of the compound having the structure: ##STR186##

EXAMPLE VIII

The following spicy, floral and herbal type formulae are prepared:

    ______________________________________                                                          Parts by Weight                                             Ingredient          VIII (A) VIII (B)                                         ______________________________________                                        Geranium Bourbon    20.0     20.0                                             Rosemary Oil Spanish                                                                              10.0     10.0                                             Lavender Oil Barreme                                                                              10.0     10.0                                             Thyme Oil White     10.0     10.0                                             Amyl Cinnamic Aldehyde                                                                            10.0     10.0                                             Sauge Sclaree French                                                                              5.0      5.0                                              Sandalwood Oil      5.0      5.0                                              Galbanum Oil        5.0      5.0                                              Patchouli Oil Light 5.0      5.0                                              Cedarwood Oil Light 15.0     15.0                                             Product produced according                                                                        5.0      --                                               to Example III, bulked                                                        fractions 5-11 containing                                                     and consisting of the                                                         compounds having the                                                          structures:                                                                    ##STR187##                                                                   and                                                                            ##STR188##                                                                   Product produced according                                                                        --       5.0                                              to Example V containing                                                       bulked fractions 1-9                                                          and consisting of the                                                         compounds having the                                                          structures:                                                                    ##STR189##                                                                   and                                                                            ##STR190##                                                                   ______________________________________                                    

When the compositions of matter prepared according to Example III orExample V are incorporated into the formulae at 5.0% both compositionsof matter add a pleasant fruity, tagette character to these spicy,herbal, floral type perfume formulations.

EXAMPLE IX

A jasmine formulae is produced containing the following ingredients:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Isoeugenol        2.0                                                         Benzyl Propionate 10.0                                                        Benzyl Acetate    13.0                                                        Benzyl Alcohol    14.0                                                        Benzyl Benzoate   9.0                                                         Linalool          8.0                                                         Phytol            30.0                                                        Methyl Oleate     4.0                                                         Methyl Palmitate  4.0                                                         Indole - 10% in Diethyl                                                       Phthalate         1.0                                                         Composition produced                                                                            5.0                                                         according to Example IV                                                       containing bulked                                                             fractions 7-12 and                                                            containing the compounds                                                      having the structures:                                                         ##STR191##                                                                   and                                                                            ##STR192##                                                                   ______________________________________                                    

The material produced according to Example IV incorporated into theformula above at 5.0% gives rise to the pleasant fruityness aromaundertone of this jasmine formulation.

EXAMPLE X

The following sweet, floral formula is produced:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Hexyl Cinnamic Aldehyde                                                                         12.0                                                        Benzyl Propionate 8.0                                                         Isoeugenol        2.0                                                         Indole - 10% in Diethyl                                                                         1.0                                                         Phthalate                                                                     Linalool          8.0                                                         Benzyl Acetate    8.0                                                         Vetivert Oil - Bourbon                                                                          2.0                                                         Gamma Methyl Ionone                                                                             1.0                                                         Phenyl Ethyl Alcohol                                                                            6.0                                                         Patchouli Oil Light                                                                             1.0                                                         Lavandin Abrialis 4.0                                                         Hydroxy Citronellal                                                                             4.0                                                         Bergamot Oil M.P.F.                                                                             6.0                                                         Benzyl Salicylate 13.0                                                        Musk Ambrette     8.0                                                         Coumarin          6.0                                                         Composition of matter pro-                                                                      10.0                                                        duced according to Ex. II                                                     consisting of bulked                                                          fractions 4-6 and consist-                                                    ing the compounds having                                                      the structures:                                                                ##STR193##                                                                   and                                                                            ##STR194##                                                                   ______________________________________                                    

At the 10% level in the foregoing sweet, floral formulation thecompounds having the structures: ##STR195## produced according toExample II contribute an intense and pleasant fruity, floralcy to thissweet, floral fragrance.

EXAMPLE XI

A stable lotion is prepared with the following formulations:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        poly(N,N--dimethyl-3,5-dimethyl-                                                                    1.0                                                     ene piperidinium chloride)                                                    (Merquat 100, Merck & Co., U.S.A.,                                            average molecular weight 50,000-                                              100,000,viscosity in 40% aqueous                                              solution, 10,000 cps.)                                                        cocoamidopropyl dimethyl glycine                                                                    5.7                                                     (betaine)                                                                     myristyl dimethylamine oxide                                                                        12.0                                                    stearic monoethanolamide opacifier                                                                  2.0                                                     perfume as indicated in Table III                                                                   0.5                                                     (below) giving rise to the                                                    aroma profiles as indicated in                                                Table III (below)                                                             water, colour, salts, U.V.                                                                          q.s. to 100                                             absorber                                                                      ______________________________________                                    

Two or three bottle capfuls of the above lotion held under the tapreleasing the water into the bathtub yields a copiously foamed bubblebath with no visible precipitation flocculation, or "bathtub ring" evenusing hard water. Bathing in this bath is found to have a cleansing andpleasing emollient effect on the skin as described above.

When, after immersion in this bath, the body is soaped, rinsed anddried, an even better, more long-lasting emollient, moisturizing effecton the skin is observed. The foam or bubbles are substantiallyunaffected by the soaping step, and no precipitate, flocculate or"bathtub ring", or any bothersome film or coating on the bathtub surfaceis found.

The aroma produced is as is set forth in Table III below:

                  TABLE III                                                       ______________________________________                                        Product           Aroma Profile                                               ______________________________________                                        Product produced according to                                                                   A fruity, banana and                                        Example I, bulked fractions                                                                     creamy aroma with                                           4-7 consisting of compounds                                                                     camphoraceous and                                           having the structures:                                                                          minty undertones.                                            ##STR196##                                                                   and                                                                            ##STR197##                                                                   Product produced according to                                                                   A fruity, camphoraceous                                     Example II, bulked fractions                                                                    and herbaceous aroma.                                       4-6 consisting of the compounds                                               having the structures:                                                         ##STR198##                                                                   and                                                                            ##STR199##                                                                   Product produced according to                                                                   A sweet, spicy, herbal                                      Example III, bulked fractions                                                                   woody and eucalyptol-                                       7 and 8 consisting of the                                                                       like aroma with a dis-                                      compounds having the structures:                                                                tinct calamnus undertone.                                    ##STR200##                                                                   and                                                                            ##STR201##                                                                   Product produced according to                                                                   A sweet, fruity (banana)                                    Example IV, bulked fractions                                                                    creamy and minty aroma                                      7-12 consisting of compounds                                                                    with the minty nuances                                      having the structures:                                                                          increasing in intensity                                                       on dryout.                                                   ##STR202##                                                                   and                                                                            ##STR203##                                                                   Product produced according to                                                                   A fruity, banana and                                        Example V, bulked fractions                                                                     creamy aroma profile.                                       6- 8 consisting of the compounds                                              having the structures:                                                         ##STR204##                                                                   and                                                                            ##STR205##                                                                   Product produced according to                                                                   A rum/butterscotch                                          Example VI, bulked fractions                                                                    and balsamic aroma.                                         5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR206##                                                                   and                                                                            ##STR207##                                                                   Product produced according to                                                                   A green, minty, borneol-                                    Example VII, bulked fractions                                                                   like, spicy, somewhat                                       6-9 consisting of the compounds                                                                 medicinal aroma reminis-                                    having the structures:                                                                          cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                       ##STR208##                                                                   and                                                                            ##STR209##                                                                   Fragrance formulation of                                                                        A spicy, floral, herbal                                     Example VIII (A)  aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                     Fragrance formulation of                                                                        A spicy, floral, herbal                                     Example VIII (B)  aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                     Fragrance formulation of                                                                        A jasmine aroma with a                                      Example IX        pleasant fruityness.                                        Fragrance formulation of                                                                        A sweet, floral aroma                                       Example X         with excellent fruity                                                         floralcy undertones.                                        ______________________________________                                    

EXAMPLE XII

The following formulation is prepared with results in properties and usesimilar to those described in Example XI.

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        "Merquat 100"        1.0                                                      cocoamidopropyl dimethyl glycine                                                                   8.0                                                      myristyl dimethyl amine                                                                            16.0                                                     oxide                                                                         Perfume ingredient as set forth                                                                    0.8                                                      in Table IV (below) giving                                                    rise to the aroma profiles as                                                 set forth in Table IV (below)                                                 Water                q.s. to 100                                              ______________________________________                                    

The composition is a clear liquid. Its viscosity may be increased byaddition of a lauric or myristic diethanolamide or a solublepolyethylene glycol ester such as polyethylene glycol 6000. In addition,this composition may be rendered opaque by addition of stearicmonoethanolamide stearate, polyethylene glycol 600 monostearate or aglyco amido stearate such as "Cerasynt 1P".

                  TABLE IV                                                        ______________________________________                                        Product           Aroma Profile                                               ______________________________________                                        Product produced according to                                                                   A fruity, banana and                                        Example I, bulked fractions                                                                     creamy aroma with                                           4-7 consisting of compounds                                                                     camphoraceous and                                           having the structures:                                                                          minty undertones.                                            ##STR210##                                                                   and                                                                            ##STR211##                                                                   Product produced according to                                                                   A fruity, camphoraceous                                     Example II, bulked fractions                                                                    and herbaceous aroma.                                       4-6 consisting of the compounds                                               having the structures:                                                         ##STR212##                                                                   and                                                                            ##STR213##                                                                   Product produced according to                                                                   A sweet, spicy, herbal                                      Example III, bulked fractions                                                                   woody and eucalyptol-                                       7 and 8 consisting of the                                                                       like aroma with a dis-                                      compounds having the structures:                                                                tinct calamnus undertone.                                    ##STR214##                                                                   and                                                                            ##STR215##                                                                   Product produced according to                                                                   A sweet, fruity (banana)                                    Example IV, bulked fractions                                                                    creamy and minty aroma                                      7-12 consisting of compounds                                                                    with the minty nuances                                      having the structures:                                                                          increasing in intensity                                                       on dryout.                                                   ##STR216##                                                                   and                                                                            ##STR217##                                                                   Product produced according to                                                                   A fruity, banana and                                        Example V, bulked fractions                                                                     creamy aroma profile.                                       6- 8 consisting of the compounds                                              having the structures:                                                         ##STR218##                                                                   and                                                                            ##STR219##                                                                   Product produced according to                                                                   A rum/butterscotch                                          Example VI, bulked fractions                                                                    and balsamic aroma.                                         5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR220##                                                                   and                                                                            ##STR221##                                                                   Product produced according to                                                                   A green, minty, borneol-                                    Example VII, bulked fractions                                                                   like, spicy, somewhat                                       6-9 consisting of the compounds                                                                 medicinal aroma reminis-                                    having the structures:                                                                          cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                       ##STR222##                                                                   and                                                                            ##STR223##                                                                   Fragrance formulation of                                                                        A spicy, floral, herbal                                     Example VIII (A)  aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                     Fragrance formulation of                                                                        A spicy, floral, herbal                                     Example VIII (B)  aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                     Fragrance formulation of                                                                        A jasmine aroma with a                                      Example IX        pleasant fruityness.                                        Fragrance formulation of                                                                        A sweet, floral aroma                                       Example X         with excellent fruity                                                         floralcy undertones.                                        ______________________________________                                    

EXAMPLE XIII

The following shampoo is prepared containing the following ingredients:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Tridecyloxy polyethoxy ethanol                                                                      17.3                                                    of ten ethoxy groups                                                          Polyoxyethylene (20) sorbitan                                                                       7.5                                                     monolaurate                                                                   Myristyl dimethylamine oxide                                                                        25.0                                                    (30% active)                                                                  C.sub.10 -C.sub.20 fatty acyl monoethanolamide                                                      2.5                                                     (cocomonoethanolamide)                                                        Polyacrylamide of molecular weight                                                                  0.2                                                     of about 1,500,000                                                            Hydrogen peroxide (30% aqueous                                                                      0.5                                                     solution)                                                                     Perfume ingredient as indicated at                                                                  1.0                                                     Table V (below) giving rise to                                                the aroma profiles as indicated                                               in Table V (below)                                                            Deionized water (3 micromhos/cm                                                                     46.0                                                    conductivity)                                                                 ______________________________________                                    

A shampoo of the above composition is made in the following matter.First, the tridecyloxy polyethoxy ethanol is added to a clean mixingtank, with the agitator on, and the amine oxide, polyoxyethylenesorbitan monolaurate and cocomonoethanolamine are added sequentially,with continued agitation. The mix is then heated to 68° C., until thecocomonoethanolamide is melted and/or dissolved. The hydrogen peroxidesolution is then admixed with the mentioned nonionics and mixing iscontinued for about half an hour, in which the peroxide destroys anyfree amines or other harmful impurities that may be present. The mix isthen cooled to 38° C.

In a separate mixer the polyacrylamide is gradually added to the formulaweight of deionized water, with the mixer on. Addition is effectedcarefully and slowly (the polyacrylamide is sprinkled in) to avoid theproduction of "fish eyes" in the mix. After dissolving of thepolyacrylamide the solution thereof is added to the first mixing tankwith agitation and is blended with the nonionics, such mixings being atroom temperature. Subsequently the perfume as indicated in Table V(below) giving rise to the aroma profile as set forth in Table V (below)is admixed with the balance of the composition and mixing is continuedfor another half hour.

                  TABLE V                                                         ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Product produced according to                                                                    A fruity, banana and                                       Example I, bulked fractions                                                                      creamy aroma with                                          4-7 consisting of compounds                                                                      camphoraceous and                                          having the structures:                                                                           minty undertones.                                           ##STR224##                                                                   and                                                                            ##STR225##                                                                   Product produced according to                                                                    A fruity, camphoraceous                                    Example II, bulked fractions                                                                     and herbaceous aroma.                                      4-6 consisting of the compounds                                               having the structures:                                                         ##STR226##                                                                   and                                                                            ##STR227##                                                                   Product produced according to                                                                    A sweet, spicy, herbal                                     Example III, bulked fractions                                                                    woody and eucalyptol-                                      7 and 8 consisting of the                                                                        like aroma with a dis-                                     compounds having the structures:                                                                 tinct calamnus undertone.                                   ##STR228##                                                                   and                                                                            ##STR229##                                                                   Product produced according to                                                                    A sweet, fruity (banana)                                   Example IV, bulked fractions                                                                     creamy and minty aroma                                     7-12 consisting of compounds                                                                     with the minty nuances                                     having the structures:                                                                           increasing in intensity                                                       on dryout.                                                  ##STR230##                                                                   and                                                                            ##STR231##                                                                   Product produced according to                                                                    A fruity, banana and                                       Example V, bulked fractions                                                                      creamy aroma profile.                                      6-8 consisting of the compounds                                               having the structures:                                                         ##STR232##                                                                   and                                                                            ##STR233##                                                                   Product produced according to                                                                    A rum/butterscotch                                         Example VI, bulked fractions                                                                     and balsamic aroma.                                        5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR234##                                                                   and                                                                            ##STR235##                                                                   Product produced according to                                                                    A green, minty, borneol-                                   Example VII, bulked fractions                                                                    like, spicy, somewhat                                      6-9 consisting of the compounds                                                                  medicinal aroma reminis-                                   having the structures:                                                                           cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                      ##STR236##                                                                   and                                                                            ##STR237##                                                                   Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(A)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(B)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A jasmine aroma with a                                     Example IX         pleasant fruityness.                                       Fragrance formulation of                                                                         A sweet, floral aroma                                      Example X          with excellent fruity                                                         floralcy undertones.                                       ______________________________________                                    

The product made is an excellent shampoo of satisfactory viscosity andaroma, foaming power, foam stability, low conductivity and goodshampooing effects. The viscosity is about 1,000 centipoises at 20° C.and the conductivity, using the Hach Conductivity Meter, is 750micromhos/cm. The foaming power is 250 ml and the foam stability is 22seconds, by the test method previously described. In comparison, acommercial shampoo based on triethanolamine lauryl sulphate detergenthas a conductivity of about 22,000 micromhos/cm, a viscosity of about1,500 centipoises, a foaming power of about 380 ml and a foam stabilityof 60 seconds.

In panel evaluations of the experimental shampoo compared to a differentcommercial product, in actual shampooing, the experimental formula wasadjudged significantly better in being less drying, porducing a softerfeel for the wet hair, leaving the wet hair easier to comb, being lessprone to accumulate static charges (less flyaway) and having a foam ofbetter appearance and feel. Additionally, the experimental product wasjudged better in almost all hair effect properties, with the controlonly being about equal to it in curl retention. In properties other thanthose mentioned the experimental product was better in rinsability, thecontrol was better in foam build-up rate and the foams were about equalin volume and stability.

In the shampooing described herein and in subsequent Examples the humanhair is washed on the head by wetting the hair with warm tap water atabout 42° C., applying 15 grams of shampoo to the hair, lathering itinto the hair for a minute, rinsing with warm tap water for 30 seconds,re-lathering with 7 grams of shampoo for a minute and rinsing off for 30seconds, after which the hair is towel dried and dried further with anautomatic hair dryer.

EXAMPLE XIV Fabric Freshener Composition

A fabric freshener composition is prepared as follows:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        Sodium bicarbonate 3                                                          "Kyro" EOB (Trade Mark)*                                                                         1                                                          Perfume ingredient as set                                                                        1                                                          forth in Table VI below                                                       giving rise to an aroma                                                       as set forth in Table VI                                                      below                                                                         Water              0.05                                                       ______________________________________                                    

The composition of this Example is prepared by simply mixing theingredients.

The above described composition is applied to a lightly soiled andwrinkled fabric as droplets (ca. 5.0 mm avg. size) using a trigger actonsprayer having a nozzle which is adjustable to provide compositiondroplets in the desired range. The composition is applied at a rate ofabout 1 gram of composition to about 10 grams of fabric.

The fabric is then placed in an automatic dryer and dried, with tumblingaction, at a temperature of 60° C.-80° C. for a period of 15 minutes.The fabric is rendered free of wrinkles and static, and has a freshappearance and pleasant odor profile as set forth in Table VI below.Surprisingly, the sodium bicarbonate is not visible on the refreshedfabric.

In the foregoing procedure, substantially the same results were obtainedwhen sodium carbonate is substituted for the sodium bicarbonate.

                  TABLE VI                                                        ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Product produced according to                                                                    A fruity, banana and                                       Example I, bulked fractions                                                                      creamy aroma with                                          4-7 consisting of compounds                                                                      camphoraceous and                                          having the structures:                                                                           minty undertones.                                           ##STR238##                                                                   and                                                                            ##STR239##                                                                   Product produced according to                                                                    A fruity, camphoraceous                                    Example II, bulked fractions                                                                     and herbaceous aroma.                                      4-6 consisting of the compounds                                               having the structures:                                                         ##STR240##                                                                   and                                                                            ##STR241##                                                                   Product produced according to                                                                    A sweet, spicy, herbal                                     Example III, bulked fractions                                                                    woody and eucalyptol-                                      7 and 8 consisting of the                                                                        like aroma with a dis-                                     compounds having the structures:                                                                 tinct calamnus undertone.                                   ##STR242##                                                                   and                                                                            ##STR243##                                                                   Product produced according to                                                                    A sweet, fruity (banana)                                   Example IV, bulked fractions                                                                     creamy and minty aroma                                     7-12 consisting of compounds                                                                     with the minty nuances                                     having the structures:                                                                           increasing in intensity                                                       on dryout.                                                  ##STR244##                                                                   and                                                                            ##STR245##                                                                   Product produced according to                                                                    A fruity, banana and                                       Example V, bulked fractions                                                                      creamy aroma profile.                                      6-8 consisting of the compounds                                               having the structures:                                                         ##STR246##                                                                   and                                                                            ##STR247##                                                                   Product produced according to                                                                    A rum/butterscotch                                         Example VI, bulked fractions                                                                     and balsamic aroma.                                        5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR248##                                                                   and                                                                            ##STR249##                                                                   Product produced according to                                                                    A green, minty, borneol-                                   Example VII, bulked fractions                                                                    like, spicy, somewhat                                      6-9 consisting of the compounds                                                                  medicinal aroma reminis-                                   having the structures:                                                                           cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                      ##STR250##                                                                   and                                                                            ##STR251##                                                                   Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(A)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(B)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A jasmine aroma with a                                     Example IX         pleasant fruityness.                                       Fragrance formulation of                                                                         A sweet, floral aroma                                      Example X          with excellent fruity                                                         floralcy undertones.                                       ______________________________________                                    

EXAMPLE XV Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salts of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with aromas as indicated in Table VII below areprepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50% and0.80% of the perfume ingredient as set forth in Table VII below. Thedetergents are prepared by adding a homogeneously mixing the appropriatequantity of perfume ingredient as set forth in Table VII below. Thedetergents all possess aromas as set forth in Table VII below with theintensity of each increasing with greater concentrations of the perfumeingredient as indicated in Table VII below.

                  TABLE VII                                                       ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Product produced according to                                                                    A fruity, banana and                                       Example I, bulked fractions                                                                      creamy aroma with                                          4-7 consisting of compounds                                                                      camphoraceous and                                          having the structures:                                                                           minty undertones.                                           ##STR252##                                                                   and                                                                            ##STR253##                                                                   Product produced according to                                                                    A fruity, camphoraceous                                    Example II, bulked fractions                                                                     and herbaceous aroma.                                      4-6 consisting of the compounds                                               having the structures:                                                         ##STR254##                                                                   and                                                                            ##STR255##                                                                   Product produced according to                                                                    A sweet, spicy, herbal                                     Example III, bulked fractions                                                                    woody and eucalyptol-                                      7 and 8 consisting of the                                                                        like aroma with a dis-                                     compounds having the structures:                                                                 tinct calamnus undertone.                                   ##STR256##                                                                   and                                                                            ##STR257##                                                                   Product produced according to                                                                    A sweet, fruity (banana)                                   Example IV, bulked fractions                                                                     creamy and minty aroma                                     7-12 consisting of compounds                                                                     with the minty nuances                                     having the structures:                                                                           increasing in intensity                                                       on dryout.                                                  ##STR258##                                                                   and                                                                            ##STR259##                                                                   Product produced according to                                                                    A fruity, banana and                                       Example V, bulked fractions                                                                      creamy aroma profile.                                      6-8 consisting of the compounds                                               having the structures:                                                         ##STR260##                                                                   and                                                                            ##STR261##                                                                   Product produced according to                                                                    A rum/butterscotch                                         Example VI, bulked fractions                                                                     and balsamic aroma.                                        5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR262##                                                                   and                                                                            ##STR263##                                                                   Product produced according to                                                                    A green, minty, borneol-                                   Example VII, bulked fractions                                                                    like, spicy, somewhat                                      6-9 consisting of the compounds                                                                  medicinal aroma reminis-                                   having the structures:                                                                           cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                      ##STR264##                                                                   and                                                                            ##STR265##                                                                   Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(A)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(B)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A jasmine aroma with a                                     Example IX         pleasant fruityness.                                       Fragrance formulation of                                                                         A sweet, floral aroma                                      Example X          with excellent fruity                                                         floralcy undertones.                                       ______________________________________                                    

EXAMPLE XVI Preparation of a Cologne and Handkerchief Perfume

The perfume ingredient as set forth in Table VIII below is incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 5.0%and 6.0% in 75%, 80%, 85%, 90% and 95% aqueous ethanol solutions.Distinct and definite aromas as set forth in Table VIII below areimparted to the colognes. The perfume ingredients as indicated in TableVIII below are also added to handkerchief perfumes at concentrations of15%, 20%, 25%, 30% and 35% (in 75%, 80%, 85%, 90% and 95% aqueousethanol) and aroma profiles as set forth in Table VIII are imparted tothe handkerchief perfume.

                  TABLE VIII                                                      ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Product produced according to                                                                    A fruity, banana and                                       Example I, bulked fractions                                                                      creamy aroma with                                          4-7 consisting of compounds                                                                      camphoraceous and                                          having the structures:                                                                           minty undertones.                                           ##STR266##                                                                   and                                                                            ##STR267##                                                                   Product produced according to                                                                    A fruity, camphoraceous                                    Example II, bulked fractions                                                                     and herbaceous aroma.                                      4-6 consisting of the compounds                                               having the structures:                                                         ##STR268##                                                                   and                                                                            ##STR269##                                                                   Product produced according to                                                                    A sweet, spicy, herbal                                     Example III, bulked fractions                                                                    woody and eucalyptol-                                      7 and 8 consisting of the                                                                        like aroma with a dis-                                     compounds having the structures:                                                                 tinct calamnus undertone.                                   ##STR270##                                                                   and                                                                            ##STR271##                                                                   Product produced according to                                                                    A sweet, fruity (banana)                                   Example IV, bulked fractions                                                                     creamy and minty aroma                                     7-12 consisting of compounds                                                                     with the minty nuances                                     having the structures:                                                                           increasing in intensity                                                       on dryout.                                                  ##STR272##                                                                   and                                                                            ##STR273##                                                                   Product produced according to                                                                    A fruity, banana and                                       Example V, bulked fractions                                                                      creamy aroma profile.                                      6-8 consisting of the compounds                                               having the structures:                                                         ##STR274##                                                                   and                                                                            ##STR275##                                                                   Product produced according to                                                                    A rum/butterscotch                                         Example VI, bulked fractions                                                                     and balsamic aroma.                                        5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR276##                                                                   and                                                                            ##STR277##                                                                   Product produced according to                                                                    A green, minty, borneol-                                   Example VII, bulked fractions                                                                    like, spicy, somewhat                                      6-9 consisting of the compounds                                                                  medicinal aroma reminis-                                   having the structures:                                                                           cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                      ##STR278##                                                                   and                                                                            ##STR279##                                                                   Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(A)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(B)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A jasmine aroma with a                                     Example IX         pleasant fruityness.                                       Fragrance formulation of                                                                         A sweet, floral aroma                                      Example X          with excellent fruity                                                         floralcy undertones.                                       ______________________________________                                    

EXAMPLE XVII Blueberry Flavor Formulation

The following formulation is prepared:

    ______________________________________                                        Ingredients          Parts By Weight                                          ______________________________________                                        Heliotropin          3.0                                                      Terpinenol-4 (10% in 95%                                                                           0.2                                                      aqueous food grade ethanol)                                                   Benzaldehyde         1.5                                                      Anisaldehyde         0.2                                                      Phenyl acetaldehyde  0.4                                                      Benzyl formate       0.5                                                      Benzyl acetate       2.0                                                      Cis-3-hexenyl benzoate (10%                                                                        0.5                                                      in 95% aqueous food grade                                                     ethanol)                                                                      Methyl hexanoate     2.0                                                      Hexanal              1.0                                                      Eucalyptol (1% in 95% aqueous                                                                      0.5                                                      food grade ethanol)                                                           Eugenol              0.2                                                      Acetaldehyde         3.0                                                      Ethyl acetate        21.0                                                     Ethyl butyrate       26.0                                                     Propylene glycol     38.0                                                                          100.0                                                    ______________________________________                                    

The above formulation is split into 5 portions. To the first fourportions are added at the rate of 1%, the norbornane derivatives ofTable IX. To the fifth portion nothing is added. All five formulationswith and without said norbornyl derivatives are combined with water atthe rate of 100 ppm. The flavor of the first four portions eachincluding a norbornyl derivative prepared according to the preceedingexamples as indicated in Table IX below have fruity, blueberrycharacteristics with several other nuances as indicated in Table IXbelow and are all closely similar to the flavor of wild blueberries. Itis therefore preferred to use the formulations containing the norbornylderivatives as listed in Table IX below, to the basic blueberryformulation which does not contain any of said norbornyl derivatives.

                  TABLE IX                                                        ______________________________________                                        Norbornyl Derivative                                                                            Flavor Characteristics                                      ______________________________________                                        Composition produced according                                                                  A fruity, blueberry aroma                                   to Example II consisting of                                                                     and taste.                                                  bulked fractions 4-6 contain-                                                 ing the compounds having                                                      the structures:                                                                ##STR280##                                                                   and                                                                            ##STR281##                                                                   The composition of Example III                                                                  A sweet, fruity, berry-                                     bulked fractions 7 and 8 con-                                                                   like, spicy, black pepper-                                  taining the compounds having                                                                    like, herbaceous and clove-                                 the structures:   like aroma and taste                                                          characteristic.                                              ##STR282##                                                                   and                                                                            ##STR283##                                                                   Composition of Example V                                                                        A sweet, fruity, raspberry,                                 bulked fractions 6-8 con-                                                                       vermouth-like and blueberry                                 taining the compounds hav-                                                                      aroma profile with a fruity,                                ing the structures:                                                                             raspberry and blueberry                                                       flavor profile.                                              ##STR284##                                                                   and                                                                            ##STR285##                                                                   Composition produced                                                                            A fruity, strawberry, blue-                                 according to Example VI                                                                         berry, balsamic aroma profile                               bulked fractions 5-14                                                                           with blueberry, balsamic and                                containing the compounds                                                                        bitter profile at 2ppm.                                     having the structures:                                                         ##STR286##                                                                   and                                                                            ##STR287##                                                                   ______________________________________                                    

EXAMPLE XVIII Use of Norbophane Derivatives for Raspberry Flavors

The following basic raspberry formulation is prepared:

    ______________________________________                                        Ingredients          Parts By Weight                                          ______________________________________                                        Vanillin             2                                                        Maltol               4                                                        Parahydroxy benzyl acetone                                                                         5                                                        Dimethyl sulfide     1                                                        Alpha-ionone (10% in propylene                                                                     2                                                        glycol)                                                                       Ethyl butyrate       6                                                        Ethyl acetate        16                                                       Isobutyl acetate     14                                                       Acetic acid          10                                                       Acetaldehyde         10                                                       Propylene glycol     930                                                                           1000                                                     ______________________________________                                    

The above formulation is split into five parts. Two the first fourparts, at the rate of 0.3% are added the norbornyl derivative producedaccording to the preceeding examples, as set forth in Table X below. Noadditive is added to the fifth part. The five formulations are comparedin water at the rate of 50 ppm. The four flavors containing thenorbornyl derivatives have more ripe raspberry tastes and woody,raspberry kernel characters. They also have additional nuances as setforth in Table X below. Therefore the raspberry formulations containingthe four norbornyl derivatives as additives have more natural-like andmore characteristic raspberry flavors and are therefore preferred.

                  TABLE X                                                         ______________________________________                                        Norbornyl Derivative                                                                           Flavor Profile                                               ______________________________________                                        Product produced accord-                                                                       A sweet, fruity, berry-like,                                 ing to Example III,                                                                            spicy, black pepper-like,                                    bulked fractions 7 and 8                                                                       herbaceous and clove-like                                    consisting of compounds                                                                        aroma and taste.                                             having the stuctures:                                                          ##STR288##                                                                   and                                                                            ##STR289##                                                                   Product produced according                                                                     A sweet, fruity, red berry,                                  to Example IV, bulked                                                                          raspberry-like and seedy                                     fractions 7-12 consisting                                                                      aroma profile with a sweet,                                  of the compounds having                                                                        fruity, red berry-like,                                      the structures:  raspberry-like, seedy and                                                     strawberry taste profile                                      ##STR290##                                                                   and                                                                            ##STR291##                                                                   Product produced according                                                                     A sweet, fruity, raspberry,                                  to Example V, bulked                                                                           vermouth-like and blueberry                                  fractions 6-8, consisting                                                                      aroma profile with a fruity,                                 of the compounds having                                                                        raspberry and blueberry                                      the structures:  flavor profile.                                               ##STR292##                                                                   and                                                                            ##STR293##                                                                   Product produced according                                                                     A fruity, raspberry and seedy                                to Example VII, bulked                                                                         aroma profile with a fruity,                                 fractions 6-9, consisting                                                                      raspberry, seedy and bitter                                  of the compounds having                                                                        flavor profile                                               the structures:                                                                ##STR294##                                                                   and                                                                            ##STR295##                                                                   ______________________________________                                    

EXAMPLE XIX Fruited Tapioca Cream

The contents of Ann Page Tapioca pudding mix (ingredients: sugar, cornstarch, tapioca, sodium chloride, tapioca flavor and artificial color;Net weight 138 grams) is emptied into a sauce pan. Three cups of milkare added together with one beaten egg yolk previously blendedtherewith. The resulting mix is cooked over medium heat stirringconstantly while slowly adding at the rate of 0.2%, either one of theflavor materials of Example XVII (blueberry flavor) or one of the flavormaterials of Example XVIII (raspberry blavor) each of the materialscontaining one of the norbornyl derivatives of Table IX or of Table X asthe case may be. The resulting mixture after heating, is then cooled toroom temperature in the saucepan. One egg white is slowly added to theresulting mixture together with three tablespoons of sugar. Theresulting mixture is then blended and chilled yielding pleasantlytasting blueberry or raspberry tapioca cream deserts depending uponwhether the materials of Example XVII or Example XVIII are added.

EXAMPLE XX Flavored Instant Pudding

A pudding mix (Royal Instant, Net weight 3.5 ozs. produced by StandardBrands Inc., New York, New York 10022) is intimately admixed with 2 cupsof cold fresh whole milk. To this mixture, at the rate of 0.3%, is addedone of the blueberry flavors of Example XVII containing the norbornylderivative as listed in Table IX or one of the raspberry flavors ofExample XVIII containing one of the norbornyl derivatives as listed inTable X. The resulting mixture is blended in a Waring blender for aperiod of three minutes. The resulting mixture is then cooled at 15° C.for a period of five minutes. The resulting puddings have excellentnatural blueberry or natural raspberry flavors as the case may be,depending on whether the blueberry flavors of Example XVII or whetherthe raspberry flavors of Example XVIII are used.

EXAMPLE XXI A. Powder Flavor Composition

20 Grams of one of the flavor compositions of Example XVII (containingat least one of the norbornyl derivatives of Table IX) is emulsified ina solution containing 300 grams gum acacia and 700 grams water. Theemulsion is spray-dried with a Bowen Lab Model Drier utilizing 260c.f.m. of air with an inlet temperature of 500° F., an outlettemperature of 200° F., and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients        Parts By Weight                                            ______________________________________                                        Liquid Blueberry Flavor,                                                                         20                                                         composition of Ex. XVII                                                       Propylene glycol   9                                                          Cab-O-Sil® M-5 (Brand of                                                                     5.00                                                       Silica produced by the                                                        Cabot Corp. of 125 High St.                                                   Boston, Mass. 02110;                                                          Physical Properties:                                                          Surface area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012                                                  microns                                                                       Density: 2.3 lbs./cu. ft.                                                     ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid blueberry flavor compositions(containing the norbornyl derivatives) of Example XVII with vigorousstirring, thereby resulting in a viscous liquid. 71 Parts by weight ofthe powder flavor composition of Part A, supra, is then blended into thesaid viscous liquid, with stirring, at 25° C. for a period of 30 minutesresulting in a dry, free flowing sustained release flavor powder.

EXAMPLE XXII

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the one of the liquid flavor compositionsof Example XVII (containing at least one of the norbornyl derivatives ofTable IX) is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot jell.

Coascervation is induced by adding, slowly and uniformyl 40 parts byweight of a 20% aqueous solution of sodium sulphate. During coacervationthe gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelatin is effected by pouring the heated coascervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulphate at 65° F. Theresulting jelled coascervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XXIII

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XXI. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum as a pleasant, long lastingblueberry flavor.

EXAMPLE XXIV Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XXII. 300 Parts of sucroseand 100 parts of corn syrup are then added. Mixing is effected in aribbon blender with jacketed side walls of the type manufactured by theBaker Perkins Co.

The resulting chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingblueberry flavor.

EXAMPLE XXV Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts By Weight                                                                              Ingredients                                                    ______________________________________                                        Group "A"                                                                     30.200         Glycerine                                                      15.325         Distilled Water                                                 .100          Sodium Benzoate                                                 .125          Saccharin Sodium                                                .400          Stannous Fluoride                                              Group "B"                                                                     12.500         Calcium Carbonate                                              37.200         Dicalcium Phosphate (Dihydrate)                                Group "C"                                                                     2.000          Sodium N--Lauroyl Sarcosinate                                                 (foaming agent)                                                Group "D"                                                                     1.200          Flavor Material of Ex. XVI                                     100.00 Total                                                                  ______________________________________                                    

PROCEDURE:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant blueberry flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XXVI Chewable Vitamin Tablets

The flavor material (containing norbornyl derivatives) of Table X ofExample XVIII is added to a chewable vitamin tablet formulation at therate of 10 gm/Kg which chewable vitamin tablet formulation is preparedas follows:

In a Hobart Mixer the following materials are blended to homogeneity:

    ______________________________________                                                            Gms/1000 Tablets                                          ______________________________________                                        Vitamin C (ascorbic acid) as                                                                        70.00                                                   ascorbic acid-sodium ascorbate                                                mixture 1:1                                                                   Vitamin B.sub.1 (thiamine mononitrate                                                               4.0                                                     331/3% (Hoffman La Roche)                                                     Vitamin B.sub.2 (roboflavin) as Rocoat®                                                         5.0                                                     roboflavin 331/3%                                                             Vitamin B.sub.6 (pyridoxine hydrochloride)                                                          4.0                                                     as Rocoat® pyridoxine hydrochloride                                       331/3%                                                                        Niacinamide as Rocoat® niacinamide                                                              33.0                                                    331/3%                                                                        Calcium pantothenate  11.5                                                    Vitamin B.sub.12 (cyanocobalamin) as                                                                3.5                                                     Merck 0.1% in gelatin                                                         Vitamin E (dl-alpha tocopheryl                                                                      6.6                                                     acetate) as dry Vitamin E acetate                                             331/3% Roche                                                                  d-Biotin              0.044                                                   Flavor of Example XVIII containing                                                                  (as indicated above)                                    norbornyl derivatives of Table X                                              Certified lake color  5.0                                                     Sweetener - sodium saccharin                                                                        1.0                                                     Magnesium stearate lubricant                                                                        10.0                                                    Mannitol q.s. to make 500.0                                                   ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 G dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant long lasting,consistently strong raspberry flavor for a period of 12 minutes.

EXAMPLE XXVII Chewing Tobacco

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

    ______________________________________                                        Ingredients         Parts By Weight                                           ______________________________________                                        Corn Syrup          60                                                        Licorice            10                                                        Glycerine           20                                                        Fig Juice           4.6                                                       Prune Juice         5                                                         Flavor Material of Ex. XVII                                                                       0.4                                                       Containing Norbornyl Deriva-                                                  tives as listed in Table IX                                                   ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting blueberry nuance in conjunction with the tobacco note.

EXAMPLE XXVIII Tobacco Formulation

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredient      Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco. The following flavorformulation is prepared:

    ______________________________________                                        Ingredient     Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 to 1,500ppm of one of the following norbornyl derivatives of Table XI asfollows:

                  TABLE XI                                                        ______________________________________                                        A.      Product produced according to Example II,                                     bulked fractions 4-6 consisting of the                                        compounds having the structures:                                               ##STR296##                                                                   and                                                                            ##STR297##                                                           B.      Composition of matter produced according to                                   Example III bulked fractions 7 and 8 consisting                               of the compounds having the stuctures:                                         ##STR298##                                                                   and                                                                            ##STR299##                                                           ______________________________________                                    

The control cigarettes not containing the norbornyl derivatives as setforth in Table XI and the experimental cigarettes which contain thenorbornyl derivatives as set forth in Table XI are evaluated by pairedcomparison and the results are as follows:

The experimental cigarettes, are found, on smoking, to have a sweeter,spicy, woody-oriental, clove-like taste with much more body and muchmore natural tobacco-like aroma prior to smoking and on smoking in themainstream and the sidestream. The experimental cigarettes containingthe product produced according to Example II in addition have coolingnuances. The experimental cigarettes produced containing the productproduced according to Example III also have cinnamon bark nuances priorto and on smoking in the mainstream and in the sidestream.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

Accordingly, it is concluded that the norbornyl derivatives set forth inTable XI produced according to the processes of Examples II and IIIenhance the tobacco-like taste and aroma particularly the oriental-liketaste of the blended cigarette imparting to it sweet, spicy andwoody-oriental tobacco-like nuances and in addition clove-like nuances.

EXAMPLE XXIX

The following is a description of a preferred embodiment of theinvention as carried out using a process wherein minute capsules havinga diameter in the range of 50 up to 500 microns were added to a wet webof reconstituted tobacco (weight ratio of dry web to drycapsules=1:0.04. The capsules and binder materials (weight ratio of drycapsule to dry binder=1:0.1 when placed among the tobacco fibers, wetthem and entangle with them and clothe them, thus in effect securing andbinding the capsules against migration through the sheet, therebyforming a subsident stratum. The majority of binder and associatedcapsules are caught in the sheet. Substantially no capsules migratethrough the sheet. When the wet tobacco web is dried, the binder shrinksby loss of solvent, leaving the dried polymeric binder material, and thecapsules remain in place relatively with respect to sheet thickness. Thesheets containing the capsules are then shredded and used in producingsmoking articles such as cigarettes. Such cigarettes are formed using awrapper, containing a fill of tobacco extending from one end of thewrapper to the other, and intimately admixed with the tobacco, aplurality of microcapsules each comprising an aromatic volatilesynthetic clove oil flavorant. The capsules are homogeneously spaced incontigous relationship with the tobacco such that as the burning frontof the tobacco advances the length of the tobacco article, a concomitantelevation of temperature initiates consecutive rupture of the capsules(1) releasing the volatile synthetic clove oil-containing material whichemanates with smoke from the smoking article into the smoker's mouth and(2) yielding a crackling sound audible to the human ear.

Tragacanth gum solution and starch solution were prepared in thefollowing manner:

PART A Concentrated Tragacanth Gum Solution (Binder)

4.5 Pounds of dry tragacanth gum powder were stirred into 50 gallons ofwater, using a suitable mixer. Five minutes after all the powder hadbeen added, the mixer was turned off. The tragacanth gum solution wasallowed to stir for 2 hours, and then the mixer was turned on for 5minutes. Sitting for 2 additional hours, enabled the tragacanth gum tohydrate. After five minutes, the mixer was turned off, and the 55 gallondrum was covered. Just prior to combining the tragacanth gum solutionand the capsular slurry, 50 gallons of tragacanth gum solution wasdiluted with water to 3 percent tragacanth gum on a solids basis.

PART B Starch Solution

The hydrolyzed starch solution was prepared by heating a slurry of thestarch at 190 degrees Fahrenheit for a minimum of 15 minutes to providea 1 percent by weight, starch-in-water solution.

Capsule slurries were prepared in the following manner:

PART C Preparation of Synthetic Clove Oil

A mixture is prepared containing the following ingredients:

    ______________________________________                                        Ingredient              Percentage                                            ______________________________________                                        α-Caryophyllene   2.0                                                   β-Caryophyllene    2.0                                                   γ-Caryophyllene   10.0                                                  Furfural                0.1                                                   Eugenol                 65.0                                                  Eugenyl Acetate         5.0                                                   Acetyl Eugenols         5.9                                                   Norbornol Derivatives as follows:                                             A.    Product produced according to                                                                       5.0                                                     Example II, bulked fractions                                                  4-6 consisting of the compounds                                               having the structures:                                                         ##STR300##                                                                   and                                                                            ##STR301##                                                             B.    Composition of matter produced                                                                      5.0                                                     according to Example III bulked                                               fractions 7 and 8 consisting of                                               the compounds having the structures:                                           ##STR302##                                                                   and                                                                            ##STR303##                                                             ______________________________________                                    

PART D Preparation of Capsular Slurry-Encapsulation of Synthetic CloveOil

Ten grams of gum arabic were dissolved at room temperature in 220 gramsof deionized water. The mixture was agitated until the gum arabic wasfully dissolved. In a separate 240 milliliter Erlenmeyer flask, 10.0grams of modified gelatin was mixed with 220.0 grams of deionized water.The gelatin was allowed to tumefy at room temperature and also thenwarmed in a water bath to about 40° C. With stirring so that the gelatinwas dissolved.

The gelatin solution and the gum arabic solution were poured into abeaker equipped with a stirrer. A flocculence indicating theprecipitation of the gelatin was noted. The temperature of the mixturewas decreased to 35° C. The speed of the stirrer was adjusted so that itwas turning only enough to keep the phases mixed. The pH of the mixturewas 4.50.

Into the beaker containing the mixture of gum arabic and gelatin waspoured 118.0 grams of synthetic clove oil as prepared in Part C. Thespeed of the stirrer was then adjusted to mix the colloids and the oil.The oil separated into droplets. Two drops of octyl alcohol were addedto prevent foaming. The progress of the coacervation was monitored bymeans of microscopic examination.

The temperature of the mixture was lowered to room temperature, e.g.,24° C. At the higher temperature of 31° C., colloid deposition wasobserved on the oil droplets. At 24° C., little colloid could beobserved in aqueous portions of the mixture. Deposition had ceased.Stirring was continued for 30 minutes, whereupon the reaction mixturewas cooled on an ice bath to 4° C. The reaction mixture was maintainedat this temperature for 200 minutes. (When hardening was desired, 1.0milliliters of a 25 percent glutaraldehyde in water per gram of gelatinis added.)

The internal phase of the capsules thus formed was approximately 80-90percent of the total weight of the capsules.

The capsules thus produced had diameters in the range of from 50 up to500 microns. They were coated with the binder onto a tobacco sheetmaterial which was shredded and used as a fill in the manufacture of asmoking article.

PART E Variation of the Encapsulation of Synthetic Clove Oil

A variation of the encapsulation procedure set forth immediately suprais shown below.

The solution of gum arabic was warmed to 38° C., placed in a Waringblender and stirred. The clove oil prepared in Part C was addedgradually while the speed of the blender was being increased until thesize of the clove oil droplets was approximately 50-500 microns. Themixture thus formed was poured into a 1,000 milliliter beaker containinggelatin, also at 38° C., and was stirred thoroughly. The temperature wasthen allowed to drop to room temperature and then further decreased to atemperature of 4° C. to 10° C. by means of an ice bath.

It is evident that the tobacco film or filaments can be made fromvarious types and combinations of tobacco. For instance, the tobaccosheet material can be made from relatively expensive tobacco such asLatakia in which it is highly desirous to use all waste because of thehigh price thereof. So, also, it may be formed of Burley or one or morescrap or waste cigarette type tobaccos and incorporated in accordancewith a particular cigarette manufacture's formula as if it were naturalcigarette tobacco leaves. Any desired formula can thus be maintained inaccordance with the demands of a manufacturer's particular brand usingone or more types of natural shredded tobacco leaves and admixed desiredquantities of shredded capsule containing tobacco film material orfilaments, either as a blending or flavoring medium or both or forpurposes of bulking.

In the case of the manufacture of cigarettes, according to the presentinvention, tobacco films are shredded into strands or the film is formeddirectly into filaments substantially the width of the strands ofnatural shredded tobacco and of any desired length. In the case ofcigars, the capsule containing films are use in large pieces much aslong filler tobacco and forming long filler cigars. In all cases theshredded film or filaments or film used in cigarettes and cigars can behandled either manually or by machine in the same manner as naturalshredded tobacco leaves or whole leaves or portions thereof. The amountof shredded capsule-containing reconstituted tobacco or pieces of thismaterial employed in a particular blend in cigarettes or cigars,respectively, will vary according to types of tobacco used in the sheetmaterial and the requirements oa a particular manufacture.

EXAMPLE XXX Preparation of a Detergent Composition

A total of 100 grams of detergent powder (a low phosphate contentdetergent composition which contains 12% by weight phosphate builder, 8%hardness mineral ion insensitive detergent, 0.9% by weight maleicanhydride-vinyl compound co-polymer and 2% alkylene oxide condensationproduct prepared according to Example IV at column XI, of U.S. Pat. No.4,000,080 issued on Dec. 28, 1976) is intimately admixed with 0.15 gramsof one of the perfume materials of Table XII below until a substantiallyhomogeneous composition is obtained. This composition has an aroma asset forth in Table XII below which is pleasant and long lasting:

                  TABLE XII                                                       ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Product produced according to                                                                    A fruity, banana and                                       Example I, bulked fractions                                                                      creamy aroma with                                          4-7 consisting of compounds                                                                      camphoraceous and                                          having the stuctures:                                                                            minty undertones.                                           ##STR304##                                                                   and                                                                            ##STR305##                                                                   Product produced according to                                                                    A fruity, camphoraceous                                    Example II, bulked fractions                                                                     and herbaceous aroma.                                      4-6 consisting of the compounds                                               having the structures:                                                         ##STR306##                                                                   and                                                                            ##STR307##                                                                   Product produced according to                                                                    A sweet, spicy, herbal                                     Example III, bulked fractions                                                                    woody and eucalyptol-                                      7 and 8 consisting of the                                                                        like aroma with a dis-                                     compounds having the structures:                                                                 tinct calamnus undertone.                                   ##STR308##                                                                   and                                                                            ##STR309##                                                                   Product produced according to                                                                    A sweet, fruity (banana)                                   Example IV, bulked fractions                                                                     creamy and minty aroma                                     7-12 consisting of compounds                                                                     with the minty nuances                                     having the structures:                                                                           increasing in intensity                                                       on dryout.                                                  ##STR310##                                                                   and                                                                            ##STR311##                                                                   Product produced according to                                                                    A fruity, banana and                                       Example V, bulked fractions                                                                      creamy aroma profile.                                      6-8 consisting of the compounds                                               having the structures:                                                         ##STR312##                                                                   and                                                                            ##STR313##                                                                   Product produced according to                                                                    A rum/butterscotch                                         Example VI, bulked fractions                                                                     and balsamic aroma.                                        5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR314##                                                                   and                                                                            ##STR315##                                                                   Product produced according to                                                                    A green, minty, borneol-                                   Example VII, bulked fractions                                                                    like, spicy, somewhat                                      6-9 consisting of the compounds                                                                  medicinal aroma reminis-                                   having the structures:                                                                           cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                      ##STR316##                                                                   and                                                                            ##STR317##                                                                   Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(A)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(B)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A jasmine aroma with a                                     Example IX         pleasant fruityness.                                       Fragrance formulation of                                                                         A sweet, floral aroma                                      Example X          with excellent fruity                                                         floralcy undertones.                                       ______________________________________                                    

EXAMPLE XXXI Perfumed Liquid Detergents

Concentrated liquid detergents with aromas as set forth in Table XIIIbelow are prepared containing 0.10%, 0.15%, and 0.20% of the perfumeingredients set forth in Table XIII below. They are prepared by addingand homogeneously mixing the appropriate quantity of perfume ingredientset forth in Table XIII below in a liquid detergent which is ahomogeneous single-phase heavy duty liquid detergent compositioncontaining:

a. 12.5% by weight based on the free acid form of an anionic detersivesurfactant;

b. 0.5% magnesium sulfate;

c. 12% by weight of an ethoxylated nonionic detersive surfactant;

d. 3% by weight of a water-soluble bis(styrylsulfonate)biphenylbrightener; and

e. the balance of the composition being water,

prepared according to U.S. Pat. No. 3,998,750 issued on Dec. 21, 1976.The detergents all possess aromas as described in Table XIII below:

                  TABLE XIII                                                      ______________________________________                                        Product           Aroma Profile                                               ______________________________________                                        Product produced according to                                                                   A fruity, banana and                                        Example I, bulked fractions                                                                     creamy aroma with                                           4-7 consisting of compounds                                                                     camphoraceous and                                           having the structures:                                                                          minty undertones.                                            ##STR318##                                                                   and                                                                            ##STR319##                                                                   Product produced according to                                                                   A fruity, camphoraceous                                     Example II, bulked fractions                                                                    and herbaceous aroma.                                       4-6 consisting of the compounds                                               having the structures:                                                         ##STR320##                                                                   and                                                                            ##STR321##                                                                   Product produced according to                                                                   A sweet, spicy, herbal                                      Example III, bulked fractions                                                                   woody and eucalyptol-                                       7 and 8 consisting of the                                                                       like aroma with a dis-                                      compounds having the structures:                                                                tinct calamnus undertone.                                    ##STR322##                                                                   and                                                                            ##STR323##                                                                   Product produced according to                                                                   A sweet, fruity (banana)                                    Example IV, bulked fractions                                                                    creamy and minty aroma                                      7-12 consisting of compounds                                                                    with the minty nuances                                      having the structures:                                                                          increasing in intensity                                                       on dryout.                                                   ##STR324##                                                                   and                                                                            ##STR325##                                                                   Product produced according to                                                                   A fruity, banana and                                        Example V, bulked fractions                                                                     creamy aroma profile.                                       6- 8 consisting of the compounds                                              having the structures:                                                         ##STR326##                                                                   and                                                                            ##STR327##                                                                   Product produced according to                                                                   A rum/butterscotch                                          Example VI, bulked fractions                                                                    and balsamic aroma.                                         5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR328##                                                                   and                                                                            ##STR329##                                                                   Product produced according to                                                                   A green, minty, borneol-                                    Example VII, bulked fractions                                                                   like, spicy, somewhat                                       6-9 consisting of the compounds                                                                 medicinal aroma reminis-                                    having the structures:                                                                          cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                       ##STR330##                                                                   and                                                                            ##STR331##                                                                   Fragrance formulation of                                                                        A spicy, floral, herbal                                     Example VIII (A)  aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                     Fragrance formulation of                                                                        A spicy, floral, herbal                                     Example VIII (B)  aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                     Fragrance formulation of                                                                        A jasmine aroma with a                                      Example IX        pleasant fruityness.                                        Fragrance formulation of                                                                        A sweet, floral aroma                                       Example X         with excellent fruity                                                         floralcy undertones.                                        ______________________________________                                    

EXAMPLE XXXII Preparation of Mixture of Isopropyl Esters of 5-Methyl and6-Methyl-2-Norbornane Carboxylic Acids (Thermal Non-CatalyticDiels-Alder Reaction)

Reaction: ##STR332##

Into a 500 cc high pressure stainless steel autoclave equipped withshaker are placed 140 grams of methylcyclopentadiene dimer, 200 grams ofisopropyl acrylate and 1 gram of Ionol®. The autoclave is closed andheated to 200° C. and maintained at 200° C. for a period of 10 hours. Atthe end of the 10 hour period, the autoclave is opened and the contentscooled to room temperature.

The reaction mass is then distilled on a fractional distillation columnyielding the following fractions:

    ______________________________________                                               Vapor    Liquid   Head          Weight                                 Fraction                                                                             Temp.    Temp.    Vac.    Reflux                                                                              of                                     Number °C.                                                                             °C.                                                                             mm Hg.  Ratio Fraction                               ______________________________________                                        1      57/65    107/110  3.0/2.9 9:1   14.3                                   2      64       113      1.8     9:1   12                                     3      65       118      1.6     9:1   16                                     4      68       121      1.6     9:1   18                                     5      68       126      1.6     9:1   15.5                                   6      68       138      1.6     9:1   16.8                                   7      68       153      1.6     9:1   17.8                                   8      72       169      1.4     9:1   17.8                                   9      79       177      1.4     9:1   10.1                                   10     121      209      2.0     9:1   8                                      11     124      217      2.2     9:1   14.9                                   12     128      226      2.2     9:1   14.2                                   13     119      250      2.2     9:1   8.6                                    ______________________________________                                    

FIG. 34 is the GLC profile of the reaction product prior to distillation(conditions: carbowax column programmed at 80°-220° C. at 8° C. perminute).

FIG. 35-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 34containing the compound having the structure: ##STR333##

FIG. 35-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 34containing the compound having the structure: ##STR334##

FIG. 36-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR335##

FIG. 36-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR336##

EXAMPLE XXXIII CL Preparation of Ethyl Ester of 1-; 4-; 5-; and6-Methyl-2-Norbornane-Carboxylic Acids (Non-Catalytic ThermalDiels-Alder Reaction)

Reaction: ##STR337##

Into a 1 liter autoclave is placed 400 grams of methylcyclopentadienedimer and 500 grams of ethyl acrylate. The autoclave is closed and thecontents are heated with stirring to a temperature of 200° C. andmaintained at that temperature for a period of 7 hours. The autoclavepressure is 25 psig. At the end of the 7 hour period, the autoclave isdepressurized and opened and the contents cooled to room temperature.

The contents of the autoclave are then distilled on a fractionaldistillation column yielding the following fractions:

    ______________________________________                                               Vapor   Liquid  Head           Weight                                  Fraction                                                                             Temp.   Temp.   Vac.     Reflux                                                                              of                                      Number °C.                                                                            °C.                                                                            mm. Hg.  Ratio Fraction                                ______________________________________                                        1      53/60   84/80   18/30    4:1   51                                      2      60      82      3.0      4:1   66                                      3      60      82      3.0      4:1   110                                     4      62      83      3.0      4:1   83                                      5      67      87      3.0      4:1   112                                     6      67      93      3.0      4:1   107                                     7      62      105     3.0      4:1   103                                     8      62      139     3.0      4:1   43                                      9      66      225     3.0      4:1   47                                      ______________________________________                                    

FIG. 37 is the GLC profile of the reaction product prior todistillation. Conditions: programmed at 80°-220° C. at 8° C. per minute:SE-30 column.

FIG. 38-A is the NMR spectrum for Fraction 1, Peak 1 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR338##

FIG. 38-B is the NMR spectrum for Fraction 8, Peak 2 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR339##

FIG. 39-A is the infra-red spectrum for Fraction 1, Peak 1 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR340##

FIG. 39-B is the infra-red spectrum for Fraction 8, Peak 2 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR341##

EXAMPLE XXXIV Preparation of 1-; 4-; 5-; and 6-Methyl NorbornaneCarboxylic Acid Ethel Esters

Reaction: ##STR342##

Into a high pressure bottle equipped with Parr shaker is placed 200grams of the methyl cyclopentadiene-ethyl acrylate reaction productproduced according to Example XXXIII; 50 ml isopropyl alcohol and 5grams of Raney Nickel catalyst. The contents are purged with hydrogenand the bottle is then pressurized to 50 psig. While maintaining thehydrogen pressure at between 20 and 50 psig over a period of 13 hours,the reaction mass is shaken using the Parr shaker. At the end of the 13hour period the pressure bottle is opened and the reaction mass isdistilled on a 12 inch Goodloe column yielding the following fractions:

    ______________________________________                                               Vapor   Liquid  Head           Weight                                  Fraction                                                                             Temp.   Temp.   Vac.     Reflux                                                                              of                                      Number °C.                                                                            °C.                                                                            mm. Hg.  Ratio Fraction                                ______________________________________                                        1      49/44   78/79   2.0/0.8  9:1/9:1                                                                             14.8                                    2      45      80      .35      4:1   16.8                                    3      45      80      .35      4:1   23.4                                    4      46      80      .35      4:1   24.3                                    5      46      80      .35      4:1   28.0                                    6      46      87      .35      4:1   22.3                                    7      48      88      .35      4:1   22.6                                    8      54      88      .35      4:1   16.5                                    9      51      112     .35      4:1   13.6                                    10     49      230     .35      4:1    8.6                                    ______________________________________                                    

FIG. 40-A is the NMR spectrum for Fraction 2, Peak 1 of the distillationproduct of the reaction product of Example XXXIV containing thecompounds having the structures: ##STR343##

FIG. 40-B is the NMR spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR344##

FIG. 41-A is the infra-red spectrum for Fraction 2, Peak 1 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR345##

FIG. 41-B is the infra-red spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR346##

EXAMPLE XXXV Preparation of 3,5- and 3,6-Dimethyl-2-NorborneneCarboxylic Acid Ethyl Esters

Reaction: ##EQU1##

Into a 500 cc autoclave equipped for high pressure reactions is placed175 grams of methyl cyclopentadiene dimer; 250 grams of ethyl crotonateand 1 gram of Ionol®. The autoclave is closed and with stirring heatedto 200° C. and maintained at 200° C. under pressure for a period of 10hours. The contents of the autoclave are then cooled to room temperatureand the autoclave is opened. The autoclave is then emptied of itscontents and the contents are then distilled in an 18" silver columnwith Goodloe packing yielding the following fractions:

    ______________________________________                                               Vapor   Liquid   Head          Weight                                  Fraction                                                                             Temp.   Temp.    Vac.    Reflux                                                                              of                                      Number °C.                                                                            °C.                                                                             mm. Hg. Ratio Fraction                                ______________________________________                                        1      37/39   100/110  1.0/.8  9:1   19                                      2      52      97       .8      9:1   22                                      3      52      97       .8      9:1   18                                      4      50      90       .8      9:1   19                                      5      50      90       .8      9:1   19                                      6      50      91       .7      9:1   20                                      7      50      91       .7      9:1   20                                      8      50      91       .7      9:1   20                                      9      50      93       .7      9:1   24                                      10     50      101      .7      9:1   22                                      11     50      119      .7      9:1   24                                      12     50      124      .7      9:1   22                                      13     50      143      .7      9:1   23                                      14     64      163      .7      9:1    8                                      15     96      230      .7      9:1   13                                      16     109     250      .7      9:1   10                                      ______________________________________                                    

FIG. 42 is the GLC profile of the reaction product prior todistillation.

FIG. 43-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 42of the reaction product of Example XXXV containing the compound havingthe structure: ##STR347##

FIG. 43-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 42for the reaction product of Example XXXV containing the compound havingthe structure: ##STR348##

FIG. 44-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR349##

FIG. 44-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR350##

EXAMPLE XXXVI Preparation of A Detergent Composition

A total of 100 grams of detergent powder (a low phosphate contentdetergent composition which contains 12% by weight phosphate builder, 8%hardness mineral oil insensitive detergent, 0.9% by weight maleicanhydride-vinyl compound copolymer and 2% alkylene oxide condensationproduct prepared according to Example IV at column XI, of U.S. Pat. No.4,000,080 issued on Dec. 28, 1976) is intimately admixed with 0.15 gramsof one of the perfume materials of Table XIV below until a substantiallyhomogeneous composition is obtained. This composition has an aroma asset forth in Table XIV below which is pleasant and long lasting:

                  TABLE XIV                                                       ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Isopropyl ester of 5- and                                                                        A green, fruity aroma.                                     6-methyl-5-norbornane-2-                                                      carboxylic acid (thermal                                                      non-catalytic Diels-alder                                                     reaction) prepared according                                                  to Example XXXII                                                              Ethyl esters of 1-; 4-; 5-;                                                                      A sweet, fruity, minty                                     and 6-methyl-5-norbornane-                                                                       aroma.                                                     2-carboxylic acid (thermal                                                    non-catalytic Diels-alder                                                     reaction) prepared according                                                  to Example XXXIII                                                             Ethyl ester of 1-; 4-; 5-;                                                                       a fruity, banana and                                       and 6-methyl-norbornane-2-                                                                       creamy aroma profile.                                      carboxylic acid (thermal                                                      non-catalytic Diels-alder                                                     reaction) prepared according                                                  to Example XXXIV                                                              Ethyl esters of 3,5- and                                                                         An intense, fruity,                                        3,6-dimethyl-5-norbornane-                                                                       strawberry-like, raspberry-                                2-carboxylic acid (thermal                                                                       like, reseda body-like                                     non-catalytic Diels-alder                                                                        aroma but does not have                                    reaction) prepared according                                                                     tagett nuances.                                            to Example XXXV                                                               ______________________________________                                    

EXAMPLE XXXVII Perfumed Liquid Detergents

Concentrated liquid detergents with aromas as set forth in Table XVbelow are prepared containing 0.10%, 0.15%, and 0.20% of the perfumeingredients set forth in Table XV below. They are prepared by adding andhomogeneously mixing the appropriate quantity of perfume ingredient setforth in Table XV below in a liquid detergent which is a homogeneoussingle-phase heavy duty liquid detergent composition containing:

a. 12.5% by weight based on the free acid form of an anionic detersivesurfactant;

b. 0.5% magnesium sulfate;

c. 12% by weight of an ethoxylated nonionic detersive surfactant;

d. 3% by weight of a water-soluble bis(styrylsulfonate)biphenylbrightener; and

e. the balance of the composition being water,

prepared according to U.S. Pat. No. 3,998,750 issued on Dec. 21, 1976.The detergents all possess aromas as described in Table XV below:

                  TABLE XV                                                        ______________________________________                                        Product            Aroma Profile                                              ______________________________________                                        Product produced according to                                                                    A fruity, banana and                                       Example I, bulked fractions                                                                      creamy aroma with                                          4-7 consisting of compounds                                                                      camphoraceous and                                          having the structures:                                                                           minty undertones.                                           ##STR351##                                                                   and                                                                            ##STR352##                                                                   Product produced according to                                                                    A fruity, camphoraceous                                    Example II, bulked fractions                                                                     and herbaceous aroma.                                      4-6 consisting of the compounds                                               having the structures:                                                         ##STR353##                                                                   and                                                                            ##STR354##                                                                   Product produced according to                                                                    A sweet, spicy, herbal                                     Example III, bulked fractions                                                                    woody and eucalyptol-                                      7 and 8 consisting of the                                                                        like aroma with a dis-                                     compounds having the structures:                                                                 tinct calamnus undertone.                                   ##STR355##                                                                   and                                                                            ##STR356##                                                                   Product produced according to                                                                    A sweet, fruity (banana)                                   Example IV, bulked fractions                                                                     creamy and minty aroma                                     7-12 consisting of compounds                                                                     with the minty nuances                                     having the structures:                                                                           increasing in intensity                                                       on dryout.                                                  ##STR357##                                                                   and                                                                            ##STR358##                                                                   Product produced according to                                                                    A fruity, banana and                                       Example V, bulked fractions                                                                      creamy aroma profile.                                      6-8 consisting of the compounds                                               having the structures:                                                         ##STR359##                                                                   and                                                                            ##STR360##                                                                   Product produced according to                                                                    A rum/butterscotch                                         Example VI, bulked fractions                                                                     and balsamic aroma.                                        5-14 containing and consisting                                                of the compounds having the                                                   structures:                                                                    ##STR361##                                                                   and                                                                            ##STR362##                                                                   Product produced according to                                                                    A green, minty, borneol-                                   Example VII, bulked fractions                                                                    like, spicy, somewhat                                      6-9 consisting of the compounds                                                                  medicinal aroma reminis-                                   having the structures:                                                                           cent of pepacuana bark                                                        extract with strong                                                           pepacuana bark-like under-                                                    tones.                                                      ##STR363##                                                                   and                                                                            ##STR364##                                                                   Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(A)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A spicy, floral, herbal                                    Example VIII(B)    aroma with pleasant                                                           fruity tagette character-                                                     istics.                                                    Fragrance formulation of                                                                         A jasmine aroma with a                                     Example IX         pleasant fruityness.                                       Fragrance formulation of                                                                         A sweet, floral aroma                                      Example X          with excellent fruity                                                         floralcy undertones.                                       Isopropyl ester of 5- and 6-                                                                     A green, fruity aroma.                                     methyl-5-norbornane-2-                                                        carboxylic acid (thermal                                                      non-catalytic Diels-alder                                                     reaction) prepared according                                                  to Example XXXII                                                              Ethyl esters of 1-; 4-; 5-;                                                                      A sweet, fruity, minty                                     and 6-methyl-5-norbornane-                                                                       aroma.                                                     2-carboxylic acid (thermal                                                    non-catalytic Diels-alder                                                     reaction) prepared according                                                  to Example XXXIII                                                             Ethyl ester of 1-; 4-; 5-;                                                                       A fruity, banana and                                       and 6-methyl-norbornane-2-                                                                       creamy aroma profile.                                      carboxylic acid (thermal                                                      non-catalytic Diels-alder                                                     reaction) prepared according                                                  to Example XXXIV                                                              Ethyl esters of 3,5- and                                                                         An intense, fruity,                                        3,6-dimethyl-5-norbornane-                                                                       strawberry-like, rasp-                                     2-carboxylic acid (thermal                                                                       berry-like, reseda body-                                   non-catalytic Diels-alder                                                                        like aroma but does not                                    reaction) prepared according                                                                     have tagett nuances.                                       to Example XXXV                                                               ______________________________________                                    

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a perfume composition or cologne comprising the step of adding to aperfume composition or cologne base an aroma augmenting or enhancingquantity of at least one compound defined according to the genericstructure: ##STR365## wherein the dashed line represents a carbon-carbonsingle bond or a carbon-carbon double bond; R₁ ' R₂ ' R₃ ' R₄ ' R₆ ' andR₇ ' are each selected from the group consisting of hydrogen and methyland R₅ ' is a C₁ -C₄ alkyl moiety with the provisos that:
 1. one of R₁', R₂ ', R₆ ' and R₇ ' is methyl and the other of R₁ ', R₂ ', R₆ ' andR₇ ' represents hydrogen;2. R₃ ' and R₄ ' are not both methyl;
 3. whenthe dashed line is a carbon-carbon double bond, R₁ ', R₃ ' and R₄ ' arenot all hydrogen when R₂ ' is methyl.
 2. A process for augmenting orenhancing the aroma of a perfume composition or cologne comprising thestep of adding to a perfume composition or cologne base an aromaaugmenting or enhancing quantity of a composition of matter containing amajor proportion of at least one compound defined according to thegeneric structure: ##STR366## wherein the dashed line represents acarbon-carbon single bond or a carbon-carbon double bond; R₁ ', R₂ ', R₃', R₄ ', R₆ ' and R₇ ' are each selected from the group consisting ofhydrogen and methyl and R₅ ' is a C₁ -C₄ alkyl moiety with the provisosthat:
 1. one of R₁ ', R₂ ', R₆ ' and R₇ ' is methyl and the other of R₁', R₂ ', R₆ ' and R₇ ' represents hydrogen;2. R₃ ' and R₄ ' are not bothmethyl;
 3. when the dashed line is a carbon-carbon double bond, R₁ ', R₃' and R₄ ' are not all hydrogen when R₂ ' is methylwhich composition isprepared according to a process comprising the step of intimatelyadmixing one or more methyl cyclopentadienes with at least one acrylicacid ester having the structure: ##STR367## wherein R₃ and R₄ may bemethyl or hydrogen and wherein R₅ is C₁ -C₄ alkyl in the presence of aLewis acid catalyst at a temperature from 0° to 50° C. or in the absenceof a Lewis acid catalyst at a temperature from 170° up to 250° C. at apressure greater than atmospheric pressure.
 3. The process of claim 2wherein in the process for preparing the reaction product of one or moremethyl cyclopentadienes with at least one acrylic acid ester, thereaction takes place at a temperature of from about 0° C. up to about50° C. in the presence of an alkyl aluminum chloride catalyst having thestructure:

    R".sub.m AlCl.sub.n

herein R" is C₁ -C₃ alkyl, m+n is 3, M=1 or 2 and n=1 or
 2. 4. Theprocess of claim 2 wherein in the process for reacting one or moremethyl cyclopentadienes with at least one acrylic acid ester, theprocess includes the additional step of reacting the resulting productwith hydrogen whereby the resulting product contains a major proportionof compounds wherein the dashed line is a carbon-carbon single bond.